JPH04189826A - Polyamide resin and its resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject new melt moldable resin excellent in dimensional stability, mechanical characteristics, etc., with high heat resistance by reacting 2,2-bis[4-(3--aminophenoxy)phenyl]propane, etc., with an aromatic dicarboxylic acid dihalide. CONSTITUTION:The objective resin is obtained by polycondensing a compound expressed by formula I with an aromatic dicarboxylic acid dihalide in the presence of a dehydrohalogenating agent in an organic solvent at >=60 deg.C and expressed by formula II [X is condensed polycyclic aromatic group or formula III (Y is direct bond, 0, S, SO2, CO, CH2, formula IV or V; R is 1-4C alkyl, alkoxy, halogen or phenyl; a is 0-2; b is 0-4); n is 1-1000]. Furthermore, a resin composition is prepared by blending 100 pts.wt. aforementioned resin with 5-100 pts.wt. fibrous reinforcing material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a novel aromatic polyamide that has high heat resistance and is melt-formable.

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

[Prior Art] Conventionally, aromatic polyamides obtained by reacting aromatic diamines or aromatic diisocyanates with aromatic dicarboxylic acids or derivatives thereof have various excellent physical properties and good heat resistance. It is expected that it will continue to be widely used in fields where heat resistance is required.

However, although many of the aromatic polyamides that have been developed so far have excellent mechanical properties and heat resistance, they all have the drawbacks of poor moldability and high water absorption.

For example, aromatic polyamide (
DuPont's product (trademark: evlar) has excellent properties such as flame retardancy, heat resistance, high tensile strength, and high modulus of elasticity. However, this aromatic polyamide has a clear glass transition temperature and a thermal decomposition temperature of about 430°C, and the processing temperature and thermal decomposition temperature are close to each other, so it has the disadvantage that it is difficult to process when used as a molding material. was there. Therefore, it is only used in the fields of fibers produced by wet spinning or valves. However, it has a high water absorption rate of 45%, and it is clear that it will have an adverse effect on dimensional stability, insulation, soldering heat resistance, etc. when used as a base material for electrical and electronic components.

[Problems to be Solved by the Present Invention] An object of the present invention is to provide an aromatic polyamide that has excellent processability and low water absorption, in addition to the excellent heat resistance that aromatic polyamide inherently possesses, and a method for producing the same. It is.

Furthermore, it is an object of the present invention to provide a new resin composition that improves the mechanical strength and one-dimensional stability of the polyamide and also has excellent processability.

[Means for Solving the Problems] As a result of intensive studies to achieve the above-mentioned problems, the present inventors discovered a novel aromatic polyamide and its resin composition having the desired performance, and completed the present invention. reached.

That is, the present invention.

(I) (I) In the formula, X is a condensed polycyclic aromatic group or one or more groups selected from the group consisting of the following formulas. However, Y is a direct bond, -O-, -5-1CH3C
F.

-5O2-1-CO-, -CH, -1-C- or -〇-.

CH3CF.

R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen group, or a phenyl group, a is O1 or 2, and b is 0
Or represents an integer from 1 to 4.

n represents an integer from 1 to 1000. ), (2) 2,2-bis(4-(3-aminophenoxy)phenyl 1-propane and/or 2,2-bis[4
A method for producing an aromatic polyamide of the following formula (I), which is obtained by polycondensing -(4-aminophenoxy)phenyl-1-propane and an aromatic dicarboxylic acid in an organic solvent. In the formula, X is a fused polycyclic aromatic group or one or more groups selected from the group consisting of the formula.However, Y is a direct bond, -O-, -5-7H.
7F・R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen group, a phenyl group, a is O, ] or 2, b is O
Or represents an integer from 1 to 4. Also.

n represents an integer of 1 to 1000. ) (3) Formula (I) (wherein, X is a fused polycyclic aromatic group or one or more groups selected from the group consisting of the formula. However, Y is a direct bond, -〇 -1-S-1?H・
υ・R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen group, a phenyl group, a is O, 1 or 2, and b is O
Or represents an integer from 1 to 4. Also.

n represents an integer of 1 to 1000. ) A polyamide with good thermal stability and a method for producing the same, which has a repeating unit represented by as a basic skeleton and whose molecular terminals are sealed using a -valent amine, a monovalent carboxylic acid, or a carboxylic acid derivative. , (4) Formula (I) (wherein, X is a fused polycyclic aromatic group or one or more groups selected from the group consisting of formula , -〇-1-S-CH3CF
.

-SO□-1-GO-, -C)12-, -C- or -
〇, H3CF3 R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, or a phenyl group, and a is 0, ■ or 2. b is 0
Or represents an integer from 1 to 4. Also, n is! Represents an integer of -1000. ) 100 parts by weight of polyamide represented by
A polyamide resin composition comprising 5 to 100 parts by weight of a fibrous reinforcing material.

The aromatic polyamide of the present invention has the formula (
II) diamine represented by, i.e. 2,2-bis[4-(3
-aminophenoxy)phenyl]propane and/or 2,2-bis(4-(4-aminophenoxy)phenyl)propane, and polymerize the same with an aromatic dicarboxylic acid or a derivative thereof.Further, the present invention The polyamide resin composition of 2,2-bis[
It is characterized by using 4-(3-aminophenoxy)phenyl-1propane and/or 2,2-bis[4-(4-aminophenoxy)phenyl-1propane as a diamine component, and has the heat resistance originally possessed by aromatic polyamides. In addition to this, it is a thermoplastic aromatic polyamide and its resin composition that has excellent processability.

This aromatic polyamide and its resin composition.

Due to its excellent heat resistance and thermoplasticity, extrusion molding,
It can be injection molded, and is expected to be used for a variety of purposes, including as a base material for space and aircraft, a base material for electrical and electronic parts, and as a raw material for high-strength, highly heat-resistant fibers produced by melt-spinning. It is very useful.

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

Examples of cyamines that can be used in combination include 0-phenylenecyamine, m-phenylenecyamine, p-phenylenecyamine, m-aminobenzylamine, p-aminopencylamine, 2-chloro-1,2-phenylenecyamine Amine, 4-chloro-1,2-phenylenediamine,
2,3-diaminotoluene, 2,4-diaminotoluene, 2.5-diaminotoluene, 2,6-diaminotoluene, 3.4-diaminotoluene, 2-methoxy-1,4-phenylenecyamine, 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'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfoxide', 3,
4-diaminodiphenylsulfoxide, 4.4''-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 3,4°-diaminodiphenylsulfone, 4,4''-diaminodiphenylsulfone, 3.3°
-Diaminodiphenylbenzophenone, 3,4-diaminodiphenylbenzophenone, 4,4°-diaminodiphenylbenzophenone, 3,3°-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4
゛-Diamino diphenylmethane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 1.1-bis[
4-F3-aminophenoxy)phenyl]ethane, 1
．． 1-bis[4-C4-aminophenoxy)phenyl]
Ethane.

1.2-bis[4-(3-aminophenoxy)phenyl]ethane, ■, 2-bis[4-(4-aminophenoxy)phenyl]ethane, 2,2-bis[4-(3-aminophenoxy)phenyl] ] Butane, 2,2-bis(4
-(4-aminophenoxy)phenylj-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,:i, 3.3-hexafluoropropane, 1.3-bis(3-aminophenoxy)benzene, 1.3 -bis(4-aminophenoxy)benzene, l
, 4-bis(3-aminophenoxy)benzene, ■, 4
-bis(4-aminophenoxy)benzene, 4,4'-
Bis(3-aminophenoxy)biphenyl, 4,4゛-
Bis(4-aminophenoxy)biphenyl, bis[4-
(3-aminophenoxy)phenyl 1 ketone bis[4
-(4-aminophenoxy)phenyl 1 ketone, bis[
4-(3-aminophenoxy)phenyl 1 sulfide,
Bis(4-(4-aminophenoxy)phenyl 1 sulfide, bis[4-(3-aminophenoxy)phenyl 1
Sulfoxide, bis[4-(4-aminophenoxy)phenyl] sulfoxide, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, his[4-(3- aminophenoxy)phenyl 1 ether, bis[4-(4-
aminophenoxy)phenyl 1 ether, 1,4-bis[4-(3-aminophenoxy)benzoyl 1benzene, 1.3-bis[4-(3-aminophenoxy)benzoyl 1benzene, 4.4'-bisr3 -(4-aminophenoxy)benzoyl 1 diphenyl ether, 4
, 4′-bis[3-(3-aminophenoxy)benzoyl 1 diphenyl ether, 4.4°-bis[4-(4
-amino-a.

α-dimethylbenzyl)phenoxybenzophenone,
4,4′-bis[4-(4-amino-α,a-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)- Examples include a,a-dimethylpencyl]benzene, 1,3-bis[4-(4-aminophenoxy)-〇,a-dimethylpencyl]benzene, and these can be used alone or in combination of two or more types. be done.

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

An example is the method according to claims 2-4. The aromatic cyamine used in this method is 2,2-bis[4-(3
-aminophenoxy)phenyl 1-propane and/or 2,2-bis[4-(4-aminophenoxy)phenyl 1-propane. Further, as the aromatic dicarboxylic acids used, in the method according to claim 2, aromatic dicarboxylic acid cybaride is used. For example, phthalic acid dichloride, phthalic acid dibromide, methyl phthalic acid dichloride, methyl phthalic acid cybromide, ethyl phthalic acid dichloride, ethyl phthalic acid cybromide, methoxyphthalic acid dichloride, methoxyphthalic acid dibromide, ethoxyphthalic acid dichloride, ethoxyphthalic acid dichloride Acid cybromides, chlorophthalic acid dichlorides, chlorophthalic acid dibromide, bromophthalic acid dichloride, bromophthalic acid dibromide, isophthalic acid dichloride, isophthalic acid cybromide, methyl isophthalic acid dichloride, methyl isophthalic acid dibromide, ethyl isophthalic acid dichloride, Ethylisophthalic acid dibromides,
Methoxyisophthalic acid dichloride, methoxyisophthalic dibromide, ethoxyisophthalic dichloride, ethoxyisophthalic dibromide, chloroisophthalic acid dichloride, chloroisophthalic dibromide, bromoisophthalic dichloride, bromoisophthalic dibromide, terephthalic acid dichloride , terephthalic acid dibromide, methyl terephthalic acid dichloride, methyl terephthalic acid dibromide, ethyl terephthalic acid dichloride, ethyl terephthalic acid dibromide, methoxyterephthalic acid dichloride, methoxyterephthalic acid dibromide, ethoxyterephthalic acid dichloride, ethoxyterephthalic acid Dibromide, chloroterephthalic acid dichloride, chloroterephthalic acid dibromide, bromo terephthalic acid dichloride, bromo terephthalic acid dibromide, 4,4-biphenyldicarboxylic acid dichloride,
4.4'-biphenyldicarboxylic acid sibromide, 4,4
゛-Diphenyl ether dicarboxylic acid dichloride, 4.
4-diphenyl ether dicarboxylic acid sibromide, 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゛-diphenylsulfonedicarboxylic acid dichloride, 4,4゛-diphenylsulfonedicarboxylic 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-naphthalene dicarboxylic acid dichloride, 1.4
-suphthalene dicarboxylic acid cybromide, 2,3-naphthalene dicarboxylic acid dichloride, 2,3-naphthalene dicarboxylic acid cybromide, 2,6-naphthalene dicarboxylic acid dichloride, 2,6-naphthalene dicarboxylic acid dibromide, and the like. These aromatic dicarboxylic acid sybarides may be used alone or in combination of two or more.

Moreover, in the method described in claim 3, an aromatic dicarboxylic acid is used. For example, phthalic acid, methyl phthalic acids, ethyl phthalic acid, methoxyphthalic acid, ethoxyphthalic acid, chlorophthalic acid, bromophthalic acid, isophthalic acid, methyl isophthalic acid, ethyl isophthalic acid,
Methoxyisofucric acid jaws, ethoxyisophthalic acid forms, chloroisophthalic acids, bromoisophthalic acids, terephthalic acid, methyl terephthalic acids, ethyl terephthalic acids,
Methoxyterephthalic acid moiety, ethoxyterephthalic acids, chlorotilefcuric acids, promotilefcuric acids, 2,2゛-biphenyldicarboxylic acid, 4,4゛-biphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4°-diphenyl sulfide dicarboxylic acid acid, 4,
4′-Benzophenonedicarboxylic acid, 4.4′-diphenylsulfonedicarboxylic acid, 4.4′-diphenylmethanedicarboxylic acid, 2,2-his(4-carboxyphenyl)propane, 2,2-bis(4- carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 1.4-naphthalene dicarboxylic acid, 2.3
-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and the like. These aromatic dicarboxylic acids may be used alone or in combination of two or more.

Further, in the method according to claim 4, for example, dimethyl phthalate, diethyl phthalate, diethyl 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, 4,4
Dimethyl °-biphenyldicarboxylate, diethyl 4,4′-biphenyldicarboxylate, 4°4″-dipropyl biphenyldicarboxylate, diisopropyl 4.4°-biphenyldicarboxylate, dibutyl 4,4°-biphenyldicarboxylate, 4,4 -diisobutyl biphenyl ether dicarboxylate, dimethyl 4,4゛-diphenyl ether dicarboxylate, diethyl 4,4''-diphenyl ether dicarboxylate, dipropyl 4,4°-diphenyl ether dicarboxylate, diisopropyl 4,4゜-diphenyl ether dicarboxylate, 4,4° -dibutyl diphenyl ether dicarboxylate, diisobutyl 4,4'-diphenyl ether dicarboxylate, dimethyl 4,4'-diphenyl sulfide dicarboxylate, diethyl 4,4'-diphenyl sulfide dicarboxylate, dipropyl 4,4'-diphenyl sulfide dicarboxylate, 4 .4'-Diisopropyl diphenylsulfide dicarboxylate, dibutyl 4,4'-diphenylsulfide dicarboxylate, 4,4゜-
Diisobutyl diphenyl sulfide dicarboxylate, 4.
Dimethyl 4-benzophenone dicarboxylate, diethyl 4,4-benzophenone dicarboxylate, dipropyl 4,4'-benzophenone dicarboxylate, diisopropyl 4,4'-benzophenone dicarboxylate, 4,4'-benzophenone dicarboxylic acid Dibutyl, diisobutyl 4,4°-benzophenonesicarboxylate, dimethyl 4.4′-diphenylsulfonedicarboxylate, diethyl 4.4′-diphenylsulfonedicarboxylate, dipropyl 4.4°-diphenylsulfonedicarboxylate, 4, 4°-Diphenylsulfonedicarboxylic acid diisopropyl, 4,4-
Dibutyl diphenylsulfonedicarboxylate, 4.4'
-diisobutyl diphenylsulfonedicarboxylate, 4
．． Dimethyl 4'-diphenylmethanedicarboxylate, 4,
Diethyl 4°-diphenylmethanedicarboxylate, 4.
Dipropyl 4'-diphenylmethanedicarboxylate, 4,
diisopropyl 4°-diphenylmethanedicarboxylate,
Dibutyl 4゜4゛-diphenylmethanedicarboxylate 4.
Diisobutyl 4-diphenylmethanedicarboxylate, 2
,2-bis(4-methoxycarbonylphenyl)propane, 2,2-bis(4-ethoxycarbonylphenyl)propane 2.2-bis(4-propoxycarbonylphenyl)propane, 2.2-bis(4-isopropoxy) carbonylphenyl)propane, 2,2-bis(
4-butoxycarbonylphenyl)propane, 2,2-
Bis(4-imbutoxycarbonylphenyl)propane, 2,2-bis(4-methoxycarbonylphenyl)
-1,1,1,3゜3.3-hexafluoropropane,
2,2-bis(4-ethoxyluponylphenyl)
-1,1,l,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,l, 3,3.3-hexafluoropropane, dimethyl 1,4-naphthalene dicarboxylate, l
, diethyl 4-naphthalene dicarboxylate, dipropyl 1.4-naphthalene dicarboxylate, diisopropyl 1.4-naphthalene dicarboxylate, dibutyl 1.4-naphthalene dicarboxylate.

1.4-Diisobutyl naphthalene dicarboxylate, 2.3
-Dimethyl naphthalene dicarboxylate, diethyl 2,3-naphthalene dicarboxylate, dipropyl 2,3-naphthalene dicarboxylate, diisopropyl 2,3-naphthalene dicarboxylate, dibutyl 2,3-naphthalene dicarboxylate, 2,3-naphthalene dicarboxylic acid diisobutyl,
Dimethyl 2,6-naphthalene dicarboxylate, 2,6
- aromatic dicarboxylic acid sialkylates such as diethyl naphthalene dicarboxylate, dipropyl 2,6-naphthalene dicarboxylate, diisopropyl 2,6-naphthalene dicarboxylate, dibutyl 2,6-naphthalene dicarboxylate, diisobutyl 2,6-naphthalene dicarboxylate; / or diphenyl phthalate, di(fluorophenyl) phthalate, di(chlorophenyl) phthalate, bromophenyl phthalate, di(methylphenyl) phthalate neck, di(ethylphenyl) phthalate, Di(propylphenyl) phthalates, di(isopropylphenyl) phthalates, di(butylphenyl) phthalates, di(imbutylphenyl) phthalates, tert-butylphenyl phthalates, phthalates Di(methoxyphenyl) neck, di(ethoxyphenyl) phthalates, ditrophenyl phthalates), di(phenylphenyl) phthalates,
Diphenyl isophthalate, di(fluorophenyl) isophthalate, di(chlorophenyl) isophthalate, di(bromophenyl) isophthalate, di(fluorophenyl) isophthalate,
methylphenyl), di(ethylphenyl) isophthalate, di(propylphenyl) isophthalate, di(isopropylphenyl) isophthalate, di(butylphenyl) isophthalate, di(isobutylphenyl) isophthalate, Di(t-butylphenyl) isophthalate, di(methoxyphenyl) isophthalate, di(ethoxyphenyl) isophthalate, ditrophenyl isophthalate, di(phenylphenyl) isophthalate,
Diphenyl terephthalate, fluorophenyl terephthalate, di(chlorophenyl) terephthalate, di(bromophenyl) terephthalate, fluorophenyl terephthalate,
methylphenyl), di(ethylphenyl terephthalate) neck, di(propylphenyl terephthalate) jaw, di(isopropylphenyl) terephthalate: n, di(butylphenyl) terephthalate, di(isobutylphenyl) terephthalate neck , di(t-butylphenyl) terephthalate
order, di(methoxyphenyl terephthalate) order, di(ethoxyphenyl terephthalate), ditrophenyl terephthalate), di(phenylphenyl terephthalate)
H,4,4'-biphenyldicarboxylic acid diphenyl, 4
, 4'-biphenyldicarboxylic acid di(fluorophenyl), 4,4°-biphenyldicarboxylic acid di(chlorophenyl), 4,4°-biphenyldicarboxylic acid di(bromophenyl), 4,4'-biphenyldicarboxylate acid di(methylphenyl)s, 4,4°-biphenyldicarboxylic acid di(ethylphenyl)s, 4,4°-biphenyldicarboxylic acid di(propylphenyl)s, 4,4°-biphenyldicarboxylic acid di(isopropyl) phenyl),
4.4-Biphenyldicarboxylic acid (butylphenyl)
4,4゛-biphenyldicarboxylic acid di(isobutylphenyl), 4,4゛-biphenyldicarboxylic acid di(isobutylphenyl),
t-butylphenyl), 4゜4゛-biphenyldicarboxylic acid (methoxyphenyl), 4,4°-biphenyldicarboxylic acid (ethoxyphenyl), 4,4'-
ditrophenyl biphenyldicarboxylate) n, 4
．． 4°-biphenyl ether dicarboxylic acid di(phenylphenyl) neck, 4,4°-diphenyl ether dicarboxylic acid diphenyl, 4,4°-diphenyl ether dicarboxylic acid di(fluorophenyl) H,4,4'-diphenyl ether dicarboxylic acid di(chlorophenyl) ) mark, 4.4゛-
Cyphenyl ether dicarboxylic acid di(bromophenyl)
class, 4,4゛-diphenyl ether dicarboxylic acid di(methylphenyl) order, 4,4゛-diphenyl ether dicarboxylic acid di(ethylphenyl) jaw, 4,4゛-diphenyl ether dicarboxylic acid di(propylphenyl) jaw, 4
, 4゛-diphenyl ether dicarboxylic acid di(isopropylphenyl) neck, 4,4-cyphenyl ether dicarboxylic acid di(isobutylphenyl), 4.4゛-diphenyl ether dicarboxylic acid di(isobutylphenyl) neck, 4
, 4'-diphenyl ether cyclocarboxylic acid (t-butylphenyl 1, di(methoxyphenyl) B, 4.4-
Di(ethoxyphenyl) diphenyl ether dicarboxylate, 4.4°-diphenyl ether dicarboxylic acid (phenylphenyl), 4,4°-diphenyl ether dicarboxylic acid (phenylphenyl), 4.4°-diphenyl sulfide dicarboxylic acid Diphenyl, 4,4゛-diphenylsulfide dicarboxylic acid di(fluorophenyl), 4,4゛-diphenylsulfide dicarboxylic acid di(chlorophenyl) g, 4゜4゛-diphenylsulfide dicarboxylic acid di(bromophenyl) R, 4 ,4'-
Di(methylphenyl) diphenylsulfide dicarboxylate, 4,4-diphenylsulfide dicarboxylate di(methylphenyl)
ethyl phenyl) neck, 4.4°-diphenylsulfide dicarboxylic acid di(propylphenyl) neck, 4,4°-diphenylsulfide dicarboxylic acid di(isopropylphenyl) ¥14.4.4'-diphenylsulfide dicarboxylic acid di(butyl) phenyl) :L 4.4'-diphenylsulfide dicarboxylic acid di(isobutylphenyl)
ML 4,4°-diphenylsulfide dicarboxylic acid di(t-butylphenyl), 4,4゛-diphenylsulfide dicarboxylic acid di(methoxyphenyl) ML
4.4′-diphenylsulfide dicarboxylic acid di(ethoxyphenyl), 4,4°-diphenylsulfide dicarboxylic acid di(phenylphenyl)), 4,4′-diphenylsulfide dicarboxylic acid di(phenylphenyl),
4,4°-benzophenonedicarboxylic acid diphenyl, 4
, 4°-benzophenone dicarboxylic acid di(fluorophenyl), 4,4'-benzophenone dicarboxylic acid di(
chlorophenyl), 4,4°-benzophenonedicarboxylic acid di(bromophenyl) R,4,4°-benzophenonedicarboxylic acid di(methylphenyl), 4,4°
-benzophenone dicarboxylic acid di(ethylphenyl) y
2B, 4,4'-benzophenonedicarboxylic acid di(propylphenyl), 4,4'-benzophenonedicarboxylic acid di(isopropylphenyl), 4,4'-benzophenonedicarboxylic acid di(butylphenyl), 4.
4'-benzophenone dicarboxylic acid di(isobutylphenyl), 4,4'-benzophenone dicarboxylic acid di(
t-butylphenyl), 4,4°-benzophenonedicarboxylic acid di(methoxyphenyl), 4.4°-benzophenonedicarboxylic acid di(ethoxyphenyl), 4
, 4'-benzophenonedicarboxylic acid di(phenylphenyl) neck, 4'-benzophenonedicarboxylic acid di(phenylphenyl), 4.4'-diphenylsulfonedicarboxylic acid diphenyl, 4.4'-diphenylsulfonedicarboxylic acid di(phenylphenyl) (fluorophenyl) neck, 4,4'-diphenylsulfonedicarboxylic acid di(chlorophenyl), 4,4'-diphenylsulfonedicarboxylic acid di(bromophenyl), 4,4'-diphenylsulfonedicarboxylic acid di(methylphenyl) ), 4,4°-diphenylsulfonedicarboxylic acid di(ethyl phenyl), 4
．． 4'-Diphenylsulfonodicarboxylic acid (propylphenyl) ]4. r-diphenylsulfonedicarboxylic acid diisopropylphenyl) jaws, 4.4-diphenylsulfonedicarboxylic acid di(butylphenyl), 4.
4゛-Diphenylsulfonedicarboxylic acid (C isobutylphenyl)) Neck 4゜4-Diphenylsulfonedicarboxylic acid (t-butylphenyl), 4.4゛-Diphenylsulfonedicarboxylic acid di(methoxyphenyl) ρ, 4.
4'-Diphenylsulfonedicarboxylic acid di(ethoxyphenyl), 4,4'-diphenylsulfonedicarboxylic acid di(phenylphenyl), 4,4'-diphenylsulfonedicarboxylic acid di(phenylphenyl), 4,4' −
diphenylmethanedicarboxylate, 4.4°-
Diphenylmethane dicarboxylic acid (fluorophenyl)
Head, 4,4°-diphenylmethanedicarboxylic acid (chlorophenyl) neck, 4,4°-diphenylmethanedicarboxylic acid (bromophenyl) chin, 4,4°-diphenylmethanedicarboxylic acid (methylphenyl) neck, 4,4'-
Diphenylmethane dicarboxylic acid (ethylphenyl)
ML 4. l-diphenylmethanedicarboxylic acid (propylphenyl) neck, 4,4゛-diphenylmethanedicarboxylic acid di(isopropylphenyl) neck, 4,4°-diphenylmethanedicarboxylic acid (butylphenyl), 4
．． 4゛-diphenylmethanedicarboxylic acid (isobutylphenyl), 4,4°-diphenylmethanedicarboxylic acid (t-butylphenyl), 4.4°-diphenylmethanedicarboxylic acid (methoxyphenyl), 4,4
"-Diphenylmethanedicarboxylic acid di(ethoxyphenyl), 4,4"-diphenylmethanedicarboxylic acid di(ethoxyphenyl), 4,4-cyphenylmethanedicarboxylic acid di(phenylphenyl), 2,2-bis( 4-
phenoxycarbonylphenyl)propane, 2.2-
Bis+4-(fluorophenoxycarbonyl)phenyl)propanes, 2,2-bis(4-(chlorophenoxycarbonyl)phenyl)propane R,2,2-bis(
4-(bromophenoxycarbonyl)phenyl)propanes, 2.2-bis(4-(methylphenoxycarbonyl)phenyl)propane Km, 2.2-bis(I
-1 Edylphenoquinocarponyl)phenyl)propane 2,2-His(4-(Probylphenoxylponyl)phenyl)propanes 2,2-His(4-(Isobrobylphenoxyluponyl)) phenyl)propane xB,
2.2-bis(4-1phthylphenoxycarbonyl)phenyl)propane 2,2-his(4-(inbutylphenoxycarbonyl)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-C nitrophenoxycarbonyl)phenyl)propanes, 2.
2~bis+4-1 phenylphenoxycarbonyl)phenyl)propane 2.2-his(4-phenoxycarbonylphenyl)-+, +.

1.3.3.3-hexafluoropropanediphenyl,
2.2-bis(4-(fluorophenoxycarbonyl)
Phenyl l-1,1,1,3,3,3-hexafluoropropanes, 2,2-bis(4-(chlorophenoxycarbonyl)phenyl)-1,1,! , 3.3.3-hexafluoropropanes 2.2-bis+4-(bromophenoxycarbonyl)phenyl l -1,1,1,3
゜3.3-Hexafluoropropanes, 2,2-bis(4-(methylphenoxycarbonyl)phenyl) -
1,1,1,3,3,3-hexafluoropropane 9,
2.2-bis(4-(ethylphenoxycarbonyl)
phenyl)-1,1,1,3,3,3-hexafluoropropanes, 2,2-bis+4-(brobylphenoxylponyl)phenyl) -1,1,1,3,3,3
-hexafluoropropanes, 2,2-bis(4-(
isopropylphenoxycarbonyl)phenyl 1-Ll
, 1.3,3.3-hexafluoropropanes, 2,
2-bis(4-(butylphenoxycarbonyl)phenyl l-1,1,1,3,3,3-hexafluoropropanes, 2.2-bis(4-(isobutylphenoxycarbonyl)phenyl) -1,1 ,1,,3,3,3=
Hexafluoropropane order 2,2-bis(4-(t-butylphenoxycarbonyl)phenyl)-1,1,1,
3,3,3-hexafluoropropanes, 2,2-bis(4-(methoxyphenoxycarbonyl)phenyl)-
1,1,l,3,3.3-hexafluoropropanes,
2,2-bis+4-(ethoxyphenoxycarbonyl)phenyl l-1,1,l, 3,3.3-hexafluoropropanes, 2.2-bis(4-trophenoxycarbonyl)phenyl) -1, 1.l.

3,3.3-hexafluoropropanes, 2,2-bis(4-(phenylphenoxycarbonyl)phenyl)
-1,1,1,3,3,3-hexafluoropropanes, 1.4-diphenyl naphthalene dicarboxylate, 1.
4-naphthalenedicarboxylic acid di(fluorophenyl), 1.4-naphthalenedicarboxylic acid di(chlorophenyl) ff, 1.4-naphthalenedicarboxylic acid di(bromophenyl), ■, 4-naphthalenedicarboxylic acid di(methylphenyl) ) Neck, 1,4-naphthalenedicarboxylic acid di(ethylphenyl) head 61.4-naphthalenedicarboxylic acid di(propylphenyl), 1.4-naphthalenedicarboxylic acid di(isopropylphenyl) dispute,
1.4-Naphthalene dicarboxylic acid (butylphenyl)
jaws, 1,4-naphthalene dicarboxylic acid di(imbutylphenyl) jaws 1,4-naphthalene dicarboxylic acid di(t-
butylphenyl) neck, 1.4-naphthalenedicarboxylic acid di(methoxyphenyl) chin, 1.4-naphthalenedicarboxylic acid di(ethoxyphenyl) mark, 1.4-naphthalenedicarboxylic acid ditrophenyl) supra, 1.4 -Naphthalene dicarboxylic acid (phenylphenyl) 9.2.
Diphenyl 3-naphthalene dicarboxylate, Di(fluorophenyl) 2,3-naphthalene dicarboxylate, 2
, 3-naphthalene dicarboxylic acid (chlorophenyl) g
, 2,3-naphthalene dicarboxylic acid di(bromophenyl) mark, 2,3-naphthalene dicarboxylic acid di(methylphenyl), 2,3-naphthalene dicarboxylic acid di(ethylphenyl), 2,3-naphthalene Dicarboxylic acid (
2,3-naphthalene dicarboxylic acid di(isopropylphenyl) order, 2,3-naphthalene dicarboxylic acid di(isobutylphenyl) order, 2,3-naphthalene dicarboxylic acid di(isobutylphenyl) neck,
2.3-naphthalenedicarboxylic acid (t-butylphenyl), 2.3-naphthalenedicarboxylic acid (methoxyphenyl), 2.3-naphthalenedicarboxylic acid (t-butylphenyl),
ethoxyphenyl), 2,3-naphthalene dicarboxylic acid di(phenylphenyl), 2,3-naphthalene dicarboxylic acid (phenylphenyl), 2,6-naphthalene dicarboxylic acid diphenyl, 2,6-naphthalene dicarboxylic acid di(phenylphenyl), (fluorophenyl) mark, 2,6-naphthalenedicarboxylic acid di(chlorophenyl), 2.6-naphthalenedicarboxylic acid di(bromophenyl), 2,6
- di(methylphenyl) naphthalenedicarboxylates,
Di(ethylphenyl) 2,6-naphthalenedicarboxylate
2,6-naphthalenedicarboxylic acid di(propylphenyl), 2,6-naphthalenedicarboxylic acid di(isopropylphenyl) neck, 2,6-naphthalenedicarboxylic acid di(butylphenyl) jaw, 2,6-naphthalenedicarboxylate Acid di(isobutylphenyl), 2,6-naphthalenedicarboxylic acid di(t-butylphenyl), 2
, 6-nac cyclocarboxylic acid (methoxyphenyl)
Aromatic dicarboxylic acid sialylates such as 2,6-naphthalene dicarboxylic acid di(ethoxyphenyl), 2,6-naphthalene dicarboxylic acid and trophenyl), and 2,6-naphthalene dicarboxylic acid di(phenylphenyl). is used. These aromatic dicarboxylic acid esters may be used alone or in combination of two or more.

The above cyamine component and aromatic dicarboxylic acid or its derivative are polymerized in a solvent. Examples of the t8 medium 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, dimethylsulfone, sulfolane , tetramethylurea, hexamethylphosphoramide, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine, 2.6-/ethylene quinoline isoquinoline
Triethylamine, tripropylamine, tributylamine, tripentylamine, N,N-dimethylaniline, N,N-diethylaniline, dichloromethane, chloroform, carbon tetrachloride, 1.1.1=trichloroethane, 1.1.2-trichloroethane , trichlorethylene, 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, tetrahydrobilane, 1,3-dioxane, 1.4- Dioxane, anisole, phenethol benzyl ether, phenyl ether, 1.2-dimethoxyethane, bis(2-methoxyethyl)ether 1.2-bis(2-methoxyethoxy)ethane, benzene, toluene, 0-xylene,
m-xylene p-xylene diphenyl, terphenyl, benzyl chloride, nitrobenzene 2-nitrotoluene, 3-nitrotoluene, 4-nitrotoluene, chlorobenzene, 2-chlorotoluene, 3-ritetratoluene,
4-chlorotoluene, 0-dichlorobenzene p-dichlorobenzene Bromobenzene, phenol, 0-cresol m-cresol, p-cresol, 2.3-
Xylenol, 2.4-xylenol, 2.5-xylenol, 2.6-xylenol, 3,4-xylenol, 3.5-xylenol, ○-chlorophenol, p-chlorophenol, methanol, ethanol,
Examples include propatool, impropatool, butanol, isobutanol, t-butanol, cyclohexanol, pencil alcohol, water, and the like. In addition, these solvents may vary depending on the type of monomer used as a reaction raw material and the polymerization method.
They may be used alone or in combination of two or more.

When aromatic dicarboxylic acid cybaride is used as the monomer of the reaction raw material, dehydrohalogenation dehydrogenation is usually used. The halogenated water μ agents used are l-limethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, N,N-dimethylpencylamine 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, a-picoline, β-picoline, γ-pifrine 2,4-lutidine, 2,6-lutidine, quinoline, isoquinoline, sodium hydroxide, potassium hydroxide, Calcium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate.

Examples include sodium hydrogen carbonate, potassium hydrogen carbonate, calcium oxide, lithium oxide, sodium acetate, potassium acetate, ethylene oxide, propylene oxide, etc.

Furthermore, when aromatic dicarboxylic acids are used as reaction raw materials and additives, a condensing agent is usually used. Condensing agents used include sulfuric anhydride, thionyl chloride, nistyl sulfite, vicryl chloride, phosphorus pentoxide, phosphorus oxychloride, phosphoric acid ester-pyridine condensing agent, triphenylphosphine-hexachloroethane condensing agent, propyl phosphorus. Examples include acid anhydride-N-methyl-2-pyrrolidone condensing agents.

The reaction temperature varies depending on the polymerization method and the type of solvent, but is usually 300°C or less.

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 reaction raw material monomer, the polymerization method, the type of polymer, the type of dehydrohalokenating agent, the type of condensing agent, and the reaction temperature. Allow the reaction to occur for a sufficient period of time to complete the formation of Usually, 10 minutes to 24 hours is sufficient.

Through such a reaction, 2 (I) N) (wherein, X is a condensed polycyclic aromatic group or one or more groups selected from the group consisting of , -O-, -5-1?"・
? 1.R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a halogen group, a phenyl group, a is O1] or 2. b is O
Or represents an integer from 1 to 4. Moreover, n represents an integer from 1 to 1000. ) An aromatic polyamide having a repeating unit represented by:

In other words, conventionally, polyamides can be synthesized by any of the known methods such as low-temperature solution polycondensation method and direct polycondensation method.
The aromatic polyamide of the present invention can be obtained.

The aromatic polyamide of the present invention contains 2,2-bis[4-f3-aminophenoxy)phenyl]propane and/or 2,2-bis[4
-(4-Aminophenoxy)phenyl]propane and an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative such as dicarboxylic acid civalide are used.

However, in order to improve the thermal stability and moldability of aromatic polyamides, there is no problem in capping the ends of the polymer molecules using -valent carboxylic acids or carboxylic acid derivatives or monovalent amines. do not have.

Such an aromatic polyamide has 2. of the above formula (II).
Aromatic diamine mainly composed of 2-bis[4-(3-aminophenoxy)phenyl]propane and/or 2,2-bis[4-(4-aminophenoxy)phenyl]propane and aromatic dicarboxylic acid or aromatic It can be obtained by reacting a group dicarboxylic acid derivative in the presence of a -valent carboxylic acid or a carboxylic acid derivative, or a -valent amine.

That is, some of the aromatic dicarboxylic acids or aromatic dicarboxylic acid derivatives are aromatic and/or aliphatic and/or
Alternatively, it is produced by using a monocarboxylic acid derivative such as an alicyclic monocarboxylic acid or a monocarboxylic acid halide, and by replacing a part of the diamine component with an aromatic and/or aliphatic and/or alicyclic monoamine.

The monovalent carboxylic acids used in this method include:
Benzoic acid, chlorobenzoic acids, e-aroic acids, bromobenzoic acids, methylbenzoic acids, ethylbenzoic acids, methoxybenzoic acids, ethoxybenzoic acids, nitrobenzoic acids, acetylbenzoic acids, acetoxybenzoic acids, hydroxybenzoic acids, biphenylcarboxylic acids, Benzophenone carboxylic acids, diphenyl ether carboxylic acids, diphenyl sulfide carboxylic 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,
Examples include nitroacetic acid, propionic acid, butyric acid, valeric acid, caproic acid, cinnamic acid, and cyclohexanecarboxylic acid.

These monocarboxylic acids may be used alone or in combination of two or more.

In addition, monocarboxylic acid halides include benzoyl chloride, benzoyl bromide, chlorobenzoyl chlorides, chlorobenzoyl bromide order, bromobenzoyl chloride neck, bromobenzoyl bromide order, methylbenzoyl chloride jaw, methylbenzoyl bromides, ethyl Benzoyl chlorides, ethylbenzoyl bromides, methoxybenzoyl chlorides, methoxybenzoyl bromides, ethoxybenzoyl chlorides, ethoxybenzoyl bromides, nitrobenzoyl chlorides,
Nitrobenzoyl bromide neck, acetylbenzoyl chloride: 0. Acetylbenzoyl bromide, acetoxybenzoyl chloride, acetoxybenzoyl bromide, hydroxybenzoyl chloride, hydroxybenzoyl bromide, biphenylcarboxylic acid chloride,
Biphenylcarboxylic acid chlorides, benzophenonecarboxylic acid chlorides, benzophenonecarboxylic acid chlorides, diphenyl ether carboxylic acid chlorides, diphenyl ether carboxylic acid chlorides, diphenyl sulfide carboxylic acid chlorides, diphenyl sulfide carboxylic acid chlorides, diphenyl sulfone carboxylic acid chlorides , diphenylsulfonecarboxylic acid bromides,
2,2-diphenylpropanecarboxylic acid chlorides, 2
．． 2-diphenylpropanecarboxylic acid bromide neck, 2,
2-diphenyl-1,1,],]3,3.3-hexafluoropropanecarboxylic acid chloride neck 2.2-diphenyl-1,I, 1.3.3.3-hexafluoropropanecarboxylic acid chloride mark, Naphthalene carboxylic acid loride neck, naphthalene carboxylic acid bromide neck.

Acetyl chloride, acetyl bromide, chloroacetate chloride, chloroacetate bromide, dichloroacetate chloride, dichloroacetate bromide, trichloroacetate chloride, trichloroacetate bromide, fluoroacetate chloride, fluoroacetate bromide, difluoroacetate chloride, difluoroacetate bromide, trifluoroacetic acid Chloride, trifluoroacetic acid chloride, nitroacetic chloride, nitroacetic acid bromide, propionic acid chloride, propionic acid bromide, butyric acid chloride, butyric acid chloride, valeric acid chloride, valeric acid promide, caproic acid chloride, caproic acid promide, cinnamic acid chloride, cinnamon Examples include acid bromide, cyclohexanecarboxylic acid chloride, and cyclohexanecarboxylic acid bromide. These monocarboxylic acid halides may be used alone or in combination of two or more.

In addition, monocarboxylic acid esters include methyl benzoate, ammonium, ethyl fragrant, propyl benzoate, ammonium,
Isopropyl benzoate, butyl benzoate, isobutyl benzoate, phenyl benzoate, ammonium, fluorophenyl mesoate, chlorophenyl benzoate, bromophenyl benzoate, methylphenyl benzoate, ethylphenyl benzoate, benzoic acid Propylphenyls, isopropylphenyl benzoate, butylphenyl benzoate, isobutylphenyl benzoate, t-butylphenyl benzoate, methoxyphenyl benzoate, ethoxyphenyl benzoate, nitrobenzoate Phenyl jaw, phenyl phenyl benzoate, methyl chlorobenzoate, ethyl chlorobenzoate, chlorobenzoate, propyl mate, isopropyl chlorobenzoate, butyl chlorobenzoate, isobutyl chlorobenzoate, chlorobenzoic acid Acid phenyls, fluorophenyl chlorobenzoates, chlorophenyl chlorobenzoates, bromophenyl chlorobenzoates, chlorobenzoate, methylphenyl yamazoate, chlorobenzoate, ethylphenyl chlorbenzoate, propylphenyl chlorobenzoate, Isopropylphenyl chlorobenzoate, butylphenyl chlorobenzoate, isobutylphenyl chlorobenzoate, chlorobenzoate, t-butylphenyl froate, chlorobenzoate, methoxyphenyl 9oate, ethoxyphenyl chlorobenzoate, Nitrophenyl tetrabenzoate, phenyl phenyl chlorobenzoate, methyl prothenbenzoate, ethyl prothenbenzoate, propyl bromobenzoate, isopropyl prothenzoate, butyl bromobenzoate , Prosenchi, 9, isobutyl fragrant, phenyl prosenchizoate, fluorophenyl bromobenzoate, chlorophenyls prothbenzoate, bromophenyl prothbenzoate, methylphenyl bromobenzoate, Bromoan, ethyl phenyl yamazoate, prosenshi, propylphenyl rhofraction, isopropylphenyl prothbenzoate, butylphenyl bromobenzoate, isobutylphenyl prothenzoic acid, t prothenbenzoate -Butylphenyls, bromobenzoic acid, methoxyphenyl fragrant, pro-senshi, ethoxyphenyl fragrant, pro-senchi, nitrophenyl fragrant, phenyl phenyl pro-thbenzoate, methyl ammonium, (p , Methyl fragrants, Methyl ammonium, Ethyl ammonium, Methyl benzoate propyl neck, Methyl ammonium, Calligraphy, Isopropyl fragrant sign Methyl ammonium, Butyl 9oate, Methyl ammonium,
- Ibutyl fragrant, phenyl methylbenzoate, fluorophenyl methylbenzoate, chlorophenyls methylbenzoate, bromophenyl methylbenzoate, methylbenzoate,! ! , methylphenyl fragrant, methylbenzoic acid, methylbenzoic acid, ethylphenyl fragrant, propylphenyl methylbenzoate, isopropylphenyl methylbenzoate, butylphenyl methylbenzoate, isobutylphenyl methylbenzoate, t- methylbenzoate Butylphenyls, methoxyphenyl methylbenzoate, ethoxyphenyl methylbenzoate, nitrophenyl methylbenzoate, phenyl phenyl methylbenzoate, methyl ethylbenzoate, ethyl ethylbenzoate, ethyl benzoate Propyl acids, isopropyl ethyl benzoate, butyl ethyl benzoate, isobutyl ethyl benzoate, phenyl ethyl benzoate, fluorophenyl ethyl benzoate, chlorophenyl ethyl benzoate, bromophenyl ethyl benzoate Neck, ethyl anhydride, 9. Medylphenyl fragrant, ethylphenyl ethylbenzoate, propylphenyl ethylbenzoate, ethyl benzoate, isopropylphenyl yamazoate,
Ethyl benzoate, butylphenyl fluoroate, isobutylphenyl ethyl benzoate, t-butylphenyl ethyl benzoate, ethyl benzoate, methoxyphenyl monozoate, ethoxyphenyl ethyl benzoate, ethyl benzoic acid Nitrophenyl order, ethyl benzoic acid phenyl phenyl neck, methoxybenzoic acid, methyl fragrant, methoxybenzoate, ethyl fragrant, propyl methoxybenzoate, isopropyl methoxybenzoate, butyl methoxybenzoate, Isobutyl methoxybenzoate, phenyl methoxybenzoate, methoxyben, Hibiki, fluorophenyl fragrant, chlorophenyl methoxybenzoate, methoxyben, -promophenyl fragrant, methylphenyl methoxybenzoate, methoxybenzoate , ethylphenyl merzoate, methoxybenzoate, propylphenyl carbonate, isopropylphenyl methoxybenzoate, butylphenyl methoxybenzoate, methoxyammonium p
isobutylphenyl fragrant, methoxybenzoic acid butylphenyl, methoxyphenyl methoxybenzoate,
Methoxyben, C-ethoxyphenyl aromaate, nitrophenyl methoxybenzoate, methoxyben, phenyl phenyl yamazoate, ethoxyben, methyl fragrant, ethyl ethoxybenzoate, propyl ethoxybenzoate, ethoxybenzoic acid Isopropyl, butyl ethoxybenzoate,
Isobutyl ethoxybenzoate, phenyl ethoxybenzoate, fluorophenyl ethoxybenzoate, chlorophenyl ethoxybenzoate, bromophenyl ethoxybenzoate, methylphenyl ethoxybenzoate, ethylphenyl ethoxybenzoate, ethoxybenzoate Propylphenyl acute aromatics, ethoxyben, isopropylphenyl yamakoate, butylphenyl ethoxybenzoate, isobutylphenyl ethoxybenzoate, ethoxyben, t rhozoic acid
-Butylphenyl, methoxyphenyl ethoxybenzoate, ethoxyphenyl ethoxybenzoate, ethoxyben, nitrophenyl borzoate, ethoxyben, phenyl phenyl sulfate, methyl nitrobenzoate, ethyl nitrobenzoate , propyl nitrobenzoate, isopropyl nitrobenzoate, phtyl nitrobenzoate, isobutyl nitrobenzoate, phenyl nitrobenzoate, nitrobenzoate, fluorophenyl fluoroate, chlorophenyl nitrobenzoate, Bromophenyl nitrobenzoate, nitroben, methylphenyl middleborate, ethyl nitrobenzoate = ) L, i, propylphenyl nitrobenzoate, isopropylphenyl nitrobenzoate, butylphenyl nitrobenzoate, Isobutylphenyl nitrobenzoate, Mt-butylphenyl nitrobenzoate,
Methoxyphenyl nitrobenzoate, ethoxyphenyl nitrobenzoate, nitrophenyl nitrobenzoate,
Phenyl phenyl nitrobenzoates, methyl acetylbenzoate, ethyl acetylbenzoate, acetylbenzoate, propyl yamazoate, acetylbenzoate, isopropyl argentate,
Butyl acetyl benzoate, acetyl benzoate, isobutyl yamakoate, phenyl acetyl benzoate, fluorophenyl acetyl benzoate, chlorophenyl acetyl benzoate, acetyl yuriro, bromophenyl fragrant, acetyl fragrant, methyl fragrant Phenyls, ethylphenyl acetylbenzoate, propylphenyl acetylbenzoate,
Isopropylphenyl acetyl benzoate, butylphenyl acetyl benzoate, isobutylphenyl acetyl benzoate, t-butylphenyl acetyl benzoate,
Acetyl benzoate, methoxyphenyls, ethoxyphenyl acetyl benzoate, nitrophenyl acetyl benzoate, phenyl phenyl acetyl benzoate, methyl acetoxybenzoate, ethyl acetoxybenzoate , propyl acetoxybenzoate, isopropyl acetoxybenzoate, butyl acetoxybenzoate, isobutyl acetoxybenzoate, phenyl acetoxybenzoate, fluorophenyl acetoxybenzoate, chlorophenyl acetoxybenzoate, butyl acetoxybenzoate Phenyls, acetoxybenzoate, methylphenyl fragrant, ethylphenyl acetoxybenzoate, propylphenyl acetoxybenzoate, isopropylphenyl acetoxybenzoate, butylphenyl acetoxybenzoate, acetoxybenzoate, isobutylphenyl sulfate , acetoxybenzoic acid t-butylphenyls, acetoxybenzoic acid methoxyphenyls, acetoxybenzoic acid methoxyphenyls, acetoxybenzoic acid nitrophenyls, acetoxybenzoic acid phenyl phenyls, hydroxyammonium, lily, methyl fragrant, Ethyl hydroxybenzoates, propyl hydroxybenzoates, isopropyl hydroxybenzoates, butyl hydroxybenzoates, isobutyl hydroxybenzoates, phenyl hydroxybenzoates, fluorophenyl hydroxybenzoates, hydroxybenzoic acid Chlorophenyls, bromophenyl hydroxybenzoate jaw, methylphenyl hydroxybenzoate neck, ethylphenyl hydroxybenzoate, propylphenyl hydroxybenzoate, isopropylphenyl hydroxybenzoate, butylphenyl hydroxybenzoate, hydroxybenzoate ,! ! Isobutylphenyl fragrant, 9J hydroxybenzoic acid t, -1 tylphenyl zp, methoxyphenyl hydroxybenzoate, ethoxyphenyl hydroxybenzoate, nitrophenyl hydroxybenzoate, phenyl phenyl hydroxybenzoate, biphenylcarboxylic acid Methyl, ethyl biphenylcarboxylate, propyl biphenylcarboxylate, isopropyl diphenylcarboxylate, butyl biphenylcarboxylate,
Isobutyl biphenylcarboxylate neck, phenyl biphenylcarboxylate, fluorophenyl biphenylcarboxylate, chlorophenyl biphenylcarboxylate, bromophenyl biphenylcarboxylate neck, methylphenyl biphenylcarboxylate jaw, ethylphenyl biphenylcarboxylate, propylphenyl biphenylcarboxylate 1, biphenylcarboxylic acid isopropylphenyl order, biphenylcarboxylic acid butylphenyl order, biphenylcarboxylic acid inbutylphenyl order, biphenylcarboxylic acid t-butylphenyl order, biphenylcarboxylic acid methoxyphenyls, biphenylcarboxylic acid ethoxyphenyl order, biphenylcarboxylic acid Nitrophenyls, phenyl phenyl biphenylcarboxylate, methyl benzophenonecarboxylate, ethyl benzophenonecarboxylate, propyl benzophenonecarboxylate, isopropyl benzophenonecarboxylate, butyl benzophenonecarboxylate,
Isobutyl benzophenonecarboxylate, phenyl benzophenonecarboxylate, fluorophenyl benzophenonecarboxylate, chlorophenyl benzophenonecarboxylate, bromophenyl benzophenonecarboxylate, methylphenyl benzophenonecarboxylate, ethyl phenyl benzophenonecarboxylate, Propylphenyl benzophenonecarboxylate, isopropylphenyl benzophenonecarboxylate, butylphenyl benzophenonecarboxylate, isobutylphenyl benzophenonecarboxylate, t-butylphenyl benzophenonecarboxylate, methoxyphenyl benzophenonecarboxylate, ethoxy benzophenonecarboxylate phenyls,
Nitrophenyl benzophenone carboxylate order, phenyl phenyl benzophenone carboxylate jaw, methyl diphenyl ether carboxylate neck, ethyl diphenyl ether carboxylate neck, propyl diphenyl ether carboxylate mark, isopropyl diphenyl ether carboxylate neck, butyl diphenyl ether carboxylate neck, isobutyl diphenyl ether carboxylate neck , diphenyl ether carboxylic acid phenyl order, diphenyl ether carboxylic acid fluorophenyls, diphenyl ether carboxylic acid chlorophenyl neck, diphenyl ether carboxylic acid bromophenyl jaws, diphenyl ether carboxylic acid methylphenyl jaws, diphenyl ether carboxylic acid ethylphenyls, diphenyl ether carboxylic acid propylphenyls, diphenyl ether Isopropylphenyl carboxylates Diphenyl ether carboxylic acid butylphenyl, diphenyl ether carboxylic acid butylphenyl, diphenyl ether carboxylic acid isobutylphenyl, diphenyl ether carboxylic acid t-butylphenyl, diphenyl ether carboxylic acid methoxyphenyl, diphenyl ether carboxylic acid ethoxyphenyl, diphenyl ether carboxylic acid nitrophenyl, diphenyl ether Phenyl phenyl carboxylate, methyl sulfide carboxylate, ethyl diphenyl sulfide carboxylate, propyl diphenyl sulfide carboxylate, isopropyl diphenyl sulfide carboxylate, butyl diphenyl sulfide carboxylate, isobutyl diphenyl sulfide carboxylate, Phenyl sulfide carboxylate, fluorophenyl diphenyl sulfide carboxylate, chlorophenyl diphenyl sulfide carboxylate, bromophenyl diphenyl sulfide carboxylate, methyl phenyl diphenyl sulfide carboxylate, ethylphenyl diphenyl sulfide carboxylate, diphenyl sulfide carboxylic acid Propylphenyls, isopropylphenyl diphenyl sulfide carboxylate, butylphenyl diphenyl sulfide carboxylate, isobutylphenyl diphenyl sulfide carboxylate, monobutylphenyl diphenyl sulfide carboxylate, methoxyphenyl diphenyl sulfide carboxylate, diphenyl sulfide carboxylic acid Ethoxyphenyls, nitrophenyl diphenyl sulfide carboxylates, phenyl phenyl diphenyl sulfide carboxylates, methyl diphenyl sulfone carboxylates, ethyl diphenyl sulfone carboxylates,
Propyl diphenylsulfonecarboxylate, isopropyl diphenylsulfonecarboxylate, butyl diphenylsulfonecarboxylate, isobutyl diphenylsulfonecarboxylate, phenyl diphenylsulfonecarboxylate, fluorophenyl diphenylsulfonecarboxylate, chlorophenyl diphenylsulfonecarboxylate, Bromophenyl diphenylsulfonecarboxylate, methylphenyl diphenylsulfonecarboxylate, ethylphenyl diphenylsulfonecarboxylate, propylphenyl diphenylsulfonecarboxylate, isopropylphenyl diphenyl or sulfonecarboxylate, butylphenyl diphenylsulfonecarboxylate, diphenylsulfone Isobutylphenyl carboxylate, t-butylphenyl diphenylsulfonecarboxylate, methoxyphenyl diphenylsulfonecarboxylate, methoxyphenyl diphenylsulfonecarboxylate, nitrophenyl diphenylsulfonecarboxylate, phenylphenyl diphenylsulfonecarboxylate, 2, Methyl 2-diphenylpropanecarboxylate, ethyl 2.2-diphenylpropanecarboxylate B, propyl 2.2-diphenylpropanecarboxylate, isopropyl 2.2-diphenylpropanecarboxylate, 2.2-diphenylpropanecarboxylic acid Butyls, 2.2-diphenylpropanecarboxylic acid isobutyls, 2.2-diphenylpropanecarboxylic acid phenyl jaws, 2,2-diphenylpropanecarboxylic acid fluorophenyl necks, 2.2-diphenylpropanecarboxylic acid chlorophenyls, 2, 2-diphenylpropanecarboxylic acid promophenyl button, 2.2-diphenylpropanecarboxylic acid methylphenyl jaw, 2.
2-diphenylpropanocarboxylic acid ethyl phenyl button,
2.2-diphenylpropanecarboxylic acid propylphenyl, 2.2-diphenylpropanecarboxylic acid isopropylphenyl, 2,2-diphenylpropanecarboxylic acid butylphenyl, 2.2-diphenylpropanecarboxylic acid isobutylphenyl, 2. 2-diphenylpropanecarboxylic acid t-butylphenyl R, 2,2-diphenylpropanecarboxylic acid methoxyphenyl, 2
, ethoxyphenyl 2-diphenylpropanecarboxylate, nitrophenyl 2,2-diphenylpropanecarboxylate, phenyl phenyl 2,2-diphenylpropanecarboxylate, 2,2-diphenyl-1,1,,l
, 3.3.3-hexafluoropropanecarboxylic acid methyl neck, 2.2-diphenyl-1,1゜1.3.3.3
- Ethyl hexafluoropropanecarboxylate, 2.
Propyl 2-diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylate, 0 , 2,2-diphenyl-
Butyl 1,1,1,3,3,3-hexafluoropropanecarboxylate, 2,2-diphenyl-1,1,1,
:l.

3. Isobutyl 3-hexafluoropropanecarboxylate, 2,2-diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylic acid phenyl R,2,2-
Diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylic acid fluorophyl J, Nil luster, 2,2-
diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylic acid chlorophenyl neck, 2,2-diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylic acid bromophenyl neck, Methylphenyls, ethylphenyl, 2,2-diphenyl-1,1,1,3
゜3.3-Hexafluoropropanecarboxylic acid propylphenyl neck, 2,2-diphenyl-1,1,1,:1.
3.3-hexafluoropropanecarboxylic acid isopropylphenyls, 2,2-diphenyl-1,1,1,3,
Butylphenyl 3,3-hexafluoropropanecarboxylate, 2,2-diphenyl-1,1,1,3,3,3
-Fluoropropanecarboxylic acid isobutylphenyl neck, 2,2-diphenyl-1,1,1,3,3,3
-hexafluoropropanecarboxylic acid t-butylphenyl neck, 2,2-diphenyl-1,1,1,3,3,3-
Hexafluoropropanecarboxylic acid methoxyphenyls, 2,2-diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylic acid ethoxyphenyls,
2.2-diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylic acid nitrophenyl Wi,
2.2-Diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylic acid phenyl phenyls, methyl naphthalenecarboxylate, ethyl naphthalenecarboxylate, propyl naphthalenecarboxylate, isopropyl naphthalenecarboxylate Butyl naphthalenecarboxylate, isobutyl naphthalenecarboxylate, phenyl naphthalenecarboxylate, fluorophenyl naphthalenecarboxylate, fluorophenyl naphthalenecarboxylate, bromophenyl naphthalenecarboxylate, methylphenyl naphthalenecarboxylate, naphthalene carbonate ethylphenyl acids, propylphenyl naphthalenecarboxylate, isopropylphenyl naphthalenecarboxylate, butylphenyl naphthalenecarboxylate, isobutylphenyl naphthalenecarboxylate, t-naphthalenecarboxylate
Butylphenyl neck, methoxyphenyl naphthalenecarboxylate neck, ethoxyphenyl jaw, nitrophenyl naphthalenecarboxylate neck, phenylphenyl naphthalenecarboxylate order, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, phenyl acetate, Fluorophenyl acetate production, chlorophenyl acetate production,
Bromophenyl acetate, methylphenyl acetate production, ethylphenyl acetate, propylphenyl acetate neck, isopropylphenyl acetate, butylphenyl acetate, isobutylphenyl acetate, t-butylphenyl acetate jaw, methoxyphenyl acetate neck, ethoxyphenyl acetate Neck, nitrophenyl acetate Neck, phenyl phenyl acetate, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, isopropyl chloroacetate, butyl chloroacetate, isobutyl chloroacetate, phenyl chloroacetate, fluorophenyl chloroacetate fO chlorophenyl chloroacetate , bromophenyl chloroacetate, methylphenyl chloroacetate, ethyl phenyl chloroacetate, propylphenyl tetraroacetate, isopropylphenyl tetraroacetate, butylphenyl chloroacetate, isobutylphenyl chloroacetate, chloroacetic acid t-Butylphenyl, methoxyphenyl dichloroacetate, ethoxyphenyl tetraroacetate, nitrophenyl chloroacetate, phenyl phenylphenyl chloroacetate, methyl dichloroacetate, ethyl dichloroacetate, propyl dichloroacetate, isopropyl dichloroacetate, butyl dichloroacetate, Isobutyl dichloroacetate Phenyl dichloroacetate, Fluorophenyl dichloroacetate Chlorophenyl dichloroacetate, Bromophenyl dichloroacetate, Methylphenyl dichloroacetate, Ethylphenyl dichloroacetate, Propylphenyl dichloroacetate, Isopropylphenyl dichloroacetate, Butyl dichloroacetate On phenyl, isobutylphenyl dichloroacetate, at-butylphenyl dichloroacetate, methoxyphenyl dichloroacetate, ethoxyphenyl dichloroacetate, nitrophenyl dichloroacetate, phenyl phenyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, propyl trichloroacetate , isopropyl trichloroacetate, butyl trichloroacetate, isobutyl trichloroacetate, phenyl trichloroacetate, fluorophenyl trichloroacetate, chlorophenyl trichloroacetate, trichloroacetic acid 7.

Cephenyls, methylphenyl trichloroacetates, ethylphenyl trichloroacetates, propylphenyl trichloroacetates, isopropylphenyl trichloroacetates,
Butylphenyl trichloroacetate neck, isobutylphenyl trichloroacetate neck, t-butylphenyl trichloroacetate order, methoxyphenyl trichloroacetate, ethoxyphenyl trichloroacetate order, nitrophenyl trichloroacetate neck, phenylphenyl trichloroacetate jaw, methyl fluoroacetate, fluoroacetic acid ethyl, propyl fluoroacetate,
Isopropyl fluoroacetate Butyl fluoroacetate, Isobutyl fluoroacetate, Phenyl fluoroacetate, Fluorophenyl fluoroacetate, Chlorophenyl fluoroacetate, Bromophenyl fluoroacetate, Methylphenyl fluoroacetate, Ethylphenyl fluoroacetate, Propylphenyl fluoroacetate, Isopropylphenyl fluoroacetates, butylphenyl fluoroacetates, isobutylphenyl fluoroacetates, t-butylphenyl fluoroacetates, methoxyphenyl fluoroacetates, ethoxyphenyls fluoroacetates, nitrophenyl fluoroacetates, phenyl phenyl fluoroacetates, Methyl difluoroacetate, ethyl difluoroacetate, propyl difluoroacetate, isopropyl difluoroacetate, butyl difluoroacetate, isobutyl difluoroacetate, phenyl difluoroacetate, fluorophenyl difluoroacetate, chlorophenyl difluoroacetate, bromophenyl difluoroacetate,
Methylphenyl difluoroacetates, ethylphenyl difluoroacetate, propylphenyl difluoroacetate, isopropylphenyl difluoroacetate, butylphenyl difluoroacetate, isobutylphenyl difluoroacetate, t-butylphenyl difluoroacetate, methoxyphenyl difluoroacetate, Ethoxyphenyl difluoroacetate, nitrophenyl difluoroacetate, phenyl phenyl difluoroacetate, methyl trifluoroacetate 1
-ethyl trifluoroacetate, propyl trifluoroacetate,
Isopropyl trifluoroacetate, butyl trifluoroacetate, isobutyl trifluoroacetate, phenyl trifluoroacetate, fluorophenyl trifluoroacetate, chlorophenyl trifluoroacetate, bromophenyl trifluoroacetate, methylphenyl trifluoroacetate, trifluoroacetic acid Ethylphenyls, propylphenyl trifluoroacetates, isopropylphenyl trifluoroacetates, butylphenyl trifluoroacetates, imbutylphenyl trifluoroacetates, t-butylphenyl trifluoroacetates, methoxyphenyl trifluoroacetates, Ethoxyphenyl fluoroacetate neck, nitrophenyl trifluoroacetate jaw, phenyl phenyl trifluoroacetate jaw Methyl nitroacetate, ethyl nitroacetate, propyl nitroacetate, isopropyl nitroacetate, butyl nitroacetate, isobutyl nitroacetate, phenyl nitroacetate, nitroacetic acid Fluorophels, chlorophenyl nitroacetate, bromophenyl nitroacetate, methylphenyl nitroacetate, ethylphenyl nitroacetate, propylphenyl nitroacetate, isopropylphenyl nitroacetate, butylphenyl nitroacetate, isobutylphenyl nitroacetate , t-butylphenyl nitroacetate, methoxyphenyl nitroacetate, ethoxyphenyl nitroacetate, nitrophenyl nitroacetate, phenyl phenyl nitroacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, propion butyl acid, isobutyl propionate, phenyl propionate, fluorophenyl propionate,
Lorophenyl propionate, Bromophenyl propionate, Methylphenyl propionate, Ethylphenyl propionate, Propylphenyl propionate, Isopropylphenyl propionate, Butylphenyl propionate, Imbutylphenyl propionate, Propion t-butylphenyl acids, methoxyphenyl propionate, ethoxyphenyl propionate,
Nitrophenyl propionate, phenyl phenyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate,
Isopropyl butyrate, butyl butyrate, isobutyl butyrate.

Phenyl butyrate, fluorophenyl butyrate, chlorophenyl butyrate, bromophenyl butyrate, methylphenyl butyrate, ethylphenyl butyrate, propylphenyl butyrate,
Isopropylphenyl butyrate, butylphenyl butyrate,
Isobutylphenyl butyrate, t-butylphenyl butyrate, methoxyphenyl butyrate, ethoxyphenyl butyrate,
r! Nitrophenyl octate, phenyl phenyl butyrate,
Methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, phenyl valerate, fluorophenyl valerate jaw, chlorophenyl valerate neck, bromophenyl valerate jaw, methyl valerate Phenyl, ethyl phenyl valerate, propylphenyl valerate, isopropylphenyl valerate, butylphenyl valerate, isobutylphenyl valerate, t valerate
-Butylphenyl, methoxyphenyl valerate, ethoxyphenyl valerate, nitrophenyl valerate, phenyl phenyl valerate, methyl caproate, ethyl caproate, propyl caproate, isopropyl caproate, butyl caproate, caproic acid Isobutyl, phenyl caproate, fluorophenyl caproate, chlorophenyl caproate, bromophenyl caproate, methylphenyl caproate neck, ethylphenyl caproate mark, propylphenyl caproate jaw, isopropylphenyl caproate, butyl caproate Phenyls, isobutylphenyl caproate, t-butylphenyl caproate, methoxyphenyl caproate, ethoxyphenyls caproate, nitrophenyl caproate, phenyl phenyl caproate, methyl cinnamate, ethyl cinnamate, cinnamon Propyl acid, isopropyl cinnamate, butyl cinnamate, isobutyl cinnamate, phenyl cinnamate, fluorophenyl cinnamate, chlorophenyl cinnamate, bromophenyl cinnamate, methylphenyl cinnamate, ethyl phenyl cinnamate, cinnamic acid Propylphenyls, isopropylphenyl cinnamate head, butylphenyl cinnamate neck, isobutylphenyl cinnamate, monobutylphenyl cinnamate, methoxyphenyl cinnamate, ethoxyphenyl cinnamate neck,
Nitrophenyl cinnamate, phenyl phenyl cinnamate,
Methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, propyl cyclohexanecarboxylate, isopropyl cyclohexanecarboxylate, butyl cyclohexanecarboxylate, isobutyl cyclohexanecarboxylate, phenyl cyclohexanecarboxylate, fluorophenyl cyclohexanecarboxylate, chlorophenyl cyclohexanecarboxylate, cyclohexanecarboxylate Bromophenyl acids, methylphenyl cyclohexanecarboxylate, ethylphenyl cyclohexanecarboxylate,
Propylphenyl cyclohexanecarboxylate, isopropylphenyl cyclohexanecarboxylate, butylphenyl cyclohexanecarboxylate, isobutylphenyl cyclohexanecarboxylate, monobutylphenyl cyclohexanecarboxylate, methoxyphenyl cyclohexanecarboxylate, ethoxyphenyl cyclohexanecarboxylate , nitrophenyl cyclohexanecarboxylate, phenyl phenyl cyclohexanecarboxylate, and the like. These monocarboxylic acid esters may be used alone or in combination of two or more.

The amount of monocarboxylic acids used is the aromatic diamine 1
0.001-1.0 mol per mole.

If it is less than 0.001 mol, viscosity increases during high-temperature molding, causing a decrease in molding processability. Moreover, if it exceeds 1.0 mol, the ei mechanical properties will deteriorate. The preferred amount used is a ratio of 0.01 to 0.05 mol.

In addition, when using a -valent amine, for example, aniline, 0-toluidine, m-t-luidine, p-toluidine, 2.3-xylidine, 2.4-xylidine, 2
, 5-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, 0-chloroaniline, m
-Chloroaniline, p-chloroaniline, 0-bromoaniline, m-bromoaniline, p-bromoaniline, 0
- Nitroaniline, m-nitroaniline, p-nitroaniline, 0-anisidine, m-anisidine, p-anisidine, 0-phenetidine, m-phenetidine, p-phenetidine, 0-aminophenol, m-aminephenol, p- Aminophenol, 0-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, 0-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl , 2-aminophenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide , 4-aminophenyl phenyl sulfide, 2-aminophenyl phenyl sulfone, 3-aminophenyl phenyl sulfone, 4-aminophenyl phenyl sulfone, 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, ■-aminoanthracene.

2-aminoanthracene, 9-aminoanthracene, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, pentylamine, dibenthylamine , benzylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine and the like. These monoamines may be used alone or in combination of 2f1 or more.

The amount of monoamine used is the aromatic dicarboxylic acid 1
0.001 to 10 moles per mole.

If it is less than 0.001 mol, viscosity increases during high-temperature molding, causing a decrease in molding processability. Moreover, if it exceeds 1.0 mol, mechanical properties will deteriorate. The preferred usage amount is
The proportion is 0.1 to 0.5 mole.

The aromatic polyamide and its resin composition of the present invention can be subjected to melt molding. In this case, it is also possible to blend other thermoplastic resins in appropriate amounts depending on the purpose, as long as the purpose of the present invention is not impaired. Thermoplastic resins that can be blended include polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polyimide, polysulfone, polyethersulfone,
Examples include polyetherketone, polyetheretherketone, polyphenylene or ruphide, polyamideimide, polyetherimide, and modified polyphenylene oxide. Further, it is also possible to blend a thermosetting resin or a filler to an extent that does not impair the purpose of the invention. Examples of thermosetting resins include phenol resins and epoxy resins.6 Examples of fillers include graphite, carborundum, silica powder, molybdenum disulfide, wear resistance improvers such as fluorine resins, glass fibers, carbon fibers, etc. Poron fiber, silicon carbide fiber, carbon whisker, asbestos,
Reinforcing materials such as metal fibers and ceramic fibers, flame retardant improving agents such as antimony trioxide, magnesium carbonate, and calcium carbonate, electrical property improving materials such as clay and mica, and improving tracking resistance of asbestos, silica, and graphite. materials, acid resistance improvers such as barium sulfate, silica, calcium metasilicate, thermal conductivity improvers such as iron powder, zinc powder, aluminum powder, copper powder, etc., glass peas, talc, diatomaceous earth, alumina, shirasu balloon, etc. Hydrated alumina, metal oxides, colorants, etc.

Various types of fibrous reinforcing materials are used in the present invention, including glass fibers, carbon fibers, potassium titanate fibers, aromatic polyamide fibers, silicon carbide fibers, alumina fibers, boron fibers, ceramic fibers, etc. However, glass fibers, carbon fibers, potassium titanate fibers, and aromatic polyamide fibers are particularly preferably used.

The glass fibers used in the present invention are made by rapidly cooling molten glass while drawing it using various methods to form thin fibers with a predetermined diameter. This refers to rovings, etc. that are tied together into a bundle, and any of these can be used in the present invention. For the glass fiber, a silane coupling agent such as aminosilane or epoxysilane, chromic chloride, or other surface treatment agent depending on the purpose can be used to impart affinity to the base resin of the present invention. The length of the glass fiber in the present invention greatly affects the physical properties of the molded product obtained and the workability during production of the molded product. Generally, as the length of the glass fiber increases, the physical properties of the molded article improve, but on the contrary, the workability during production of the molded article deteriorates. Therefore, in the present invention, glass fibers having a length in the range of 0.1 to 6 mm, preferably 0.3 to 4 mm, are preferable because the physical properties and workability of the molded product are well balanced.

In addition, the carbon fiber used in the present invention refers to high elasticity and high strength fiber obtained by carbonizing polyacrylonitrile, petroleum pitch, etc. as main raw materials.6 In the present invention, both polyacrylonitrile and petroleum pitch are used as fibers. Can be used. Carbon fibers having an appropriate diameter and appropriate aspect ratio (length/diameter ratio) are used depending on the reinforcing effect and mixability.

The diameter of carbon fiber is usually 5 to 20 μm, especially 8 to 15 μm.
It is preferable to have a diameter of about m. Also, the aspect ratio is 1 to 60.
0, and preferably about 100 to 350, especially depending on the reinforcing effect and mixability. If the aspect ratio is small, there will be no reinforcing effect, and if the aspect ratio is large, the mixing property will be poor, making it impossible to obtain a good molded product.
Surface treatment agents such as those treated with epoxy resins, polyamide resins, polycarbonate resins, polyacetal resins, etc., as well as those using other known surface treatment agents depending on the purpose, may also be used.

In addition, the potassium titanate fiber used in the present invention is a type of high-strength fiber (whisker), and its chemical composition is as follows:
It is an acicular crystal based on 0.6TiO□, 206T10□, and H20, and its typical melting point is 1300-1350.
It is ℃. Average fiber length is 5-50um, average fiber diameter is 0
05 to 10 μm is applied, but the average fiber length is 2
Preferably, the fiber diameter is 0 to 30 μm, and the average fiber diameter is O1 to 0.3 μm. The potassium titanate fibers can normally be used without any treatment, but in order to have affinity with the base resin of the present invention, they may be treated with a silane coupling agent such as aminosilane or epoxysilane, chromic chloride, or other surface treatment depending on the purpose. agents can be used.

Furthermore, the aromatic polyamide fiber used in the present invention is a relatively newly developed heat-resistant organic fiber, and its many unique characteristics are expected to be utilized in various fields.

For example, typical examples include those with the following structural formulas.

At least one type or a mixture of two or more of these may be used.

Example) DuPont trademark, 6vlar (2) HHOO I Ill II Example) DuPont trademark, Nomex Teijin trademark Conex There are other aromatic polyamide fibers with various skeletons depending on structural isomerism at the ortho, meta, and para positions, among which (I ) is the most preferable heat-resistant organic fiber in the present invention because of its high softening and melting points.

For glass fibers and carbon fibers, if the amount is less than 5 parts by weight, the reinforcing effect peculiar to glass fibers or carbon fibers, which is a feature of the present invention, cannot be obtained. On the other hand, if 100 parts by weight or more is used, the fluidity of the composition during molding will deteriorate, making it difficult to obtain a satisfactory molded product. For potassium titanate fibers, if the amount is less than 5 parts by weight, the improvement in mechanical properties at high temperatures, which is a feature of the present invention, is insufficient. On the other hand, if the amount is too large, dispersion during melt mixing becomes insufficient, fluidity becomes low, and molding under normal conditions becomes difficult, which is not preferable. The preferred amount used is 10 to 100 parts by weight.

If the amount of aromatic polyamide fiber is less than 5 parts by weight, a composition with excellent moldability and mechanical strength, which are the characteristics of the present invention, cannot be obtained. If 100 parts by weight or more is used, the fluidity of the composition during molding will deteriorate, making it difficult to obtain a satisfactory molded product. The preferred amount used 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 preferred.

(I) Polyamide powder and fibrous reinforcement are mixed in a mortar Henschel mixer, drum blender, tumbler blender,
The mixture is premixed using a ball mill, ribbon blender, etc., and then kneaded using a commonly known melt mixer, heated roll, etc., and then made into pellets or powder.

(2) Polyamide powder is dissolved or suspended in an organic solvent in advance, and the fiber reinforcing material is immersed in this solution or suspension,
Thereafter, the solvent is removed in a hot air oven and the mixture is pelletized or powdered. In this case, as a solvent, for example, N
, N-dinutylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-
Dimethylmethoxyacetamide, N-methyl-2-pyrrolidone 1,3=dimethyl-2-e, midazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2
-bis(2-methoxyethoxy)ethane, bis[2-(
Examples include 2-methoxyethoxy)ethyl]ether, tetrahydrofuran, l,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphosphoramide, and the like. Further, 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 □, or a rotational molding method and is put into practical use.

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

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

Logarithmic viscosity, after dissolving 0.50 g of polyamide powder in hexamethylphosphoric acid triamide + 00 + sβ, 35°C
Measured at.

Glass transition temperature fTgl・DSC (Shimadzu DT-40 series, fixed at 111 with DSC-41 cap.

5% weight dehumidification temperature: DTA-TG (Shimadzu DT
-40 series, measured with DTG-40 cap.

Melt viscosity: Measured with a load of 100 kg using Shimadzu Koka flow tester CFT500A.

Example 1 41.052 g (0.10 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl-1-propane and N-methyl- After charging and dissolving 500 g of 2-pyrrolidone, 24.29 g fo (24 mol) of triethylamine was added and the mixture was cooled to 5°C. Thereafter, the stirring was strengthened and terephthalic acid chloride (20.30 g fO, 10 mol) was charged, and stirring was continued at room temperature for 3 hours. The viscous polymer solution thus obtained was discharged into methanol under vigorous stirring to precipitate a white powder. After filtering off the white powder, it was washed with methanol and heated at 180°C for 12 hours. It was dried under reduced pressure to obtain 52.61 g (yield 97.3%) of polyamide powder.

The logarithmic viscosity of this polyamide powder is 0.93 dl/g,
Glass transition temperature is 205℃, 5% weight dehumidification temperature is 491
'C.

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

ON Calculated value (% + 77.76 5.22 518 Actual value (%l) 77.70 5,18 5.19 In addition, the infrared absorption spectrum of the obtained polyamide powder is shown in Fig. 1. This spectrum Then, around 1650c+o-' and around 1520cm-', which are the characteristic absorption bands of amide,
Significant absorption was observed.

Furthermore, after dissolving the obtained polyamide powder in N-methyl-2-pyrrolidone, it was cast on a glass plate, and 15
(Heated at I°C for 1 hour and at 250°C for 2M to obtain a colorless and transparent polyamide film. The tensile strength of this polyamide film was 1250 kg/cm" and the tensile elongation was 28%. The measurement method was Both are based on ASTM D-882.

Moreover, the water absorption rate of this film was 0.053%.

The measurement method is based on ASTM D-750-63.

Example 2 The same procedure as Example I was carried out except that terephthalic acid chloride in Example 1 was replaced with isophthalic acid chloride, and 52.82 g of polyamide powder with a logarithmic viscosity of o and 96 dl/g was prepared.
(yield 97.7%).

The glass transition temperature of this polyamide powder is 200℃, 5%
The weight and dehumidification temperature was 496°C.

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

HN Calculated value f% + 77.76 5.22 5°18 Actual value (% + 77.72 5,20 5.16 In addition, the infrared absorption spectrum of the obtained polyamide powder is shown in Figure 2. In the spectrum diagram, significant absorption was observed near 1650c+w-' and 1520cm-', which are the characteristic absorption bands of amide.

Furthermore, 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 l090kg/cm2
The tensile elongation rate was 32%, and the water absorption rate was 0.55%.

Example 3 20.30 g of terephthalic acid chloride in Example 1 (
0.15 mol) of terephthalic acid chloride (10.15 g (
0.05 mol) and 10.15 g of isophthalic acid chloride (
The same procedure as in Example 1 was carried out except that 0.05 mol) was used.
Polyamide powder with logarithmic viscosity 0.92 di/g 52.4
4 g (yield 970%) was obtained.

The glass transition temperature of this polyamide powder is 198℃, 5%
The weight and dehumidification temperature was 492°C.

A colorless and transparent polyamide film was obtained in the same manner as in Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film is 1150 kg/Cff12,
The tensile elongation rate was 30% and the water absorption rate was 0.52%.

Example 4 2,2-bis(4-(4-aminophenoxy)phenyl 1propane in Example I) was converted to 2,2-bis[4-+3
-Aminophenoxy)phenyl]propane was used in the same manner as in Example 1 to obtain 52.07 g (yield: 963%) of polyamide powder having a logarithmic viscosity of 1 Odi/g.

The glass transition temperature of this polyamide powder is 194℃, 5%
The weight and dehumidification temperature was 464°C.

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

HN Calculated value (% + 77.76 5,22 5.18 In addition, the infrared absorption spectrum of the obtained polyamide powder is shown in Figure 3. In this spectrum, 1650cli-' which is the characteristic absorption band of amide) Significant absorption was observed near and around 1520 cm-'.

Furthermore, 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 1080kg/cm2
The tensile elongation rate was 24%, and the water absorption rate was 0.60%.

Example 5 The same procedure as Example 4 was carried out except that terephthalic acid chloride in Example 4 was replaced with isophthalic acid chloride, and 52.34 g of polyamide powder with a logarithmic viscosity of 0.98 dl/g was prepared.
(yield 96.8%).

The glass transition temperature of this polyamide powder is 189℃, 5%
The weight and dehumidification temperature was 485°C.

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

HN Calculated value (%l 77.76 5,22 5.18 In addition, the infrared absorption spectrum of the obtained polyamide powder is shown in Figure 4. In this spectrum, 1650 cm-' which is the characteristic absorption band of amide) Significant absorption was observed near and around 1520 cm-'.

Furthermore, 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 1070 kg/cm
2. The tensile elongation rate was 21% and the water absorption rate was 0.55%.

Example 6 20.30 g of terephthalic acid chloride in Example 4 (
0.10 mol) to terephthalic acid chloride, 15 g
(0.05 mol) and 15 g (0.05 mol) of isophthalic acid chloride.
The same procedure as in Example 4 was carried out except that 0.05 mol) was used, and 52.50 g of polyamide powder with a logarithmic viscosity of 0.96 di/g was used.
(Yield 97.1%) was obtained.

The glass transition temperature of this polyamide powder is 182℃, 5%
The weight and dehumidification temperature was 470°C.

A colorless and transparent polyamide film was obtained in the same manner as in Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film is 1'060 kg/cm
”, the tensile elongation rate was 22%, and the water absorption rate was 0.52%.

Example 7 In a container equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere, 16.62 g of terephthalic acid (fO, 10 mol), 20.0 g of lithium chloride, 60.0 g of calcium chloride,
200g of pyridine, 62.0g of triphenyl phosphite
fO, 20 mol), N-methyl-2-pyrrolidone 100
After charging 0g and dissolving it, the temperature was raised to 120°C. 41.05 g (0.10 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was charged therein.

The mixture was stirred at 120°C for 2 hours. The viscous polymer droplets thus obtained were discharged into vigorously stirred methanol to precipitate a white powder. After filtering this white powder, it was washed with methanol and dried under reduced pressure at 180°C for 12 hours.
3.09 g (yield 98.2%) of polyamide powder was obtained.

The logarithmic viscosity of this polyamide powder is 0.90 di/g,
Glass transition temperature is 202℃, 5% weight dehumidification temperature is 490℃
It was ℃.

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

HN Calculated value (% + 77.76 5,22 5.18 Actual value (%l) 77.73 5,20 5.19 In addition, the infrared absorption spectrum of the obtained polyamide powder is shown in Figure 5. The spectrum diagram was exactly the same as that of the polyamide obtained in Example 1, and significant absorption was observed near 1650c1' and 1520cm-', which are the characteristic absorption bands of amide.

Example 8 In a container equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere, dimethyl terephthalate (19.42 g fo, 10 mol), 2,2-bisC4-(4-aminophenoxy)
phenyl]propane 41.05 g io, 10 moles),
Charge 1200g of diphenyl ether and heat at 250°C.
Stir for hours. The reaction product thus obtained was discharged into methanol with vigorous stirring to obtain a white powder. After filtering this white powder, it was washed with methanol and heated to 180°C for 12 hours.
Dry under reduced pressure for 52.07g (yield 95.3%)
Polyamide powder was obtained.

The logarithmic viscosity of this polyamide powder is 0.8.9 di/g
, the glass transition temperature is 204°C, the 15% weight loss temperature is 4
The temperature was 93°C.

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

HN Calculated value (%) 77.76 5,22 5.18 Furthermore, an infrared absorption spectrum diagram of the obtained polyamide powder is shown in FIG. This spectrum diagram.

It is exactly the same as the polyamide powder obtained in Example 1, and has a characteristic absorption band of amide around 1650 cm-' and 152 cm-'.
Remarkable absorption was observed near 0 cm-'.

Example 9 2.2-bisC4-(4-aminophenoxy)phenyl]propane (41.05 g + 0.10 mol) and N-methyl-2-pyrrolidone in a container equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere. After charging and dissolving 500g,
Triethylamine (24.29 g io, 24 moles) was added and cooled to 5°C. Thereafter, the stirring was strengthened and terephthalic acid chloride (19.29 g + 0.095 mol) was charged, and stirring was continued at room temperature for 2 hours. Thereafter, 2.11 g (10.015 mol) of benzoyl chloride was charged, and stirring was continued at room temperature for 2 hours. The resulting polymer solution was discharged into methanol with vigorous stirring 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 53.09 g.
(Yield 975%) polyamide powder was obtained.

The logarithmic viscosity of this polyamide powder was 0.45 dl/g. The melt viscosity of the obtained polyamide powder was measured and found to be 3000 poise at 300°C.

Moreover, the obtained strand was pale yellow and transparent, highly flexible, and extremely strong.

Further, the thermal stability of the polyamide obtained in this example was measured by varying the residence time in the cylinder of a flow tester.

The measurement temperature was 300°C. The results are shown in FIG. Even if the residence time in the cylinder becomes longer, the melt viscosity hardly changes, indicating that the thermal stability is good.

In addition, this polyamide powder was heated at 280℃, 150 kg/
CIl! When the heat distortion temperature of the molded product obtained by compression molding for 15 minutes was measured, it was 195°C.Measurement method 1
ASTM D-648, load 18.6 kg 7 cm”
Based on.

Example 1O 2.2-bis[4-(4-aminophenoxy)phenyl 1-propane (39.00 g io, 095 mol) and N were added in a container equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere.
After charging and dissolving 500 g of -methyl-2-pyrrolidone, 24.29 g fO, 24 mol of triethylamine was added and the mixture was cooled to 5°C. Thereafter, the stirring was strengthened and terephthalic acid chloride (20.30 g iO, 10 mol) was charged, and stirring was continued at room temperature for 2 hours. Then aniline 1
．． 40 g + 0.015 mol) and continued stirring at room temperature for 2 hours. The resulting polymer solution was drained into vigorously stirred methanol to precipitate a white powder. After filtering this white powder, it was washed with methanol and
Drying under reduced pressure at ℃ for 12 hours gave 51.03 g (yield: 96.
4%) polyamide powder was obtained.

The logarithmic viscosity of this polyamide powder was 0.44 dl/g. The melt viscosity of the obtained polyamide powder was measured and found to be 2800 poise at 300°C.

Furthermore, the obtained strand was pale yellow and transparent, highly flexible, and extremely strong.

Comparative Example 1 2.16 g of p-phenylenediamine (10020 mol) in a container equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere
After charging and dissolving 562 g of N-methyl-2-pyrrolidone, 4.86 g (1 n, 0.48 mol) of triethylamine was added, and the mixture was cooled to 5°C. After that, the stirring was increased and 3.86 g (10.019 moles) of terephthalic acid chloride was added to -
The mixture was charged in bulk and stirring was continued for 2 hours at room temperature. Thereafter, 0.443 gf of benzoyl chloride (0.003 mol) was charged, and stirring was continued for 2 hours at room temperature. The resulting polymer solution was discharged into methanol with vigorous stirring to precipitate a white powder. After separating this white powder by filtration, it was washed with methanol and dried under reduced pressure at 180°C for 12 hours.
g (yield 97.7%) of polyamide powder was obtained.

When the glass transition temperature of this polyamide powder was measured, it did not show a clear value.

Furthermore, the melt viscosity was measured at 380°C and 400°C, but no melt flow occurred at either temperature.

Comparative Example 2 Polyamide powder was synthesized in exactly the same manner as in Example 9, but without using benzoyl chloride.

The polyamide powder had a logarithmic viscosity of 0.45 dl/g.

When the residence time in the flow tester cylinder was changed and the melt viscosity was measured in the same manner as in Example 9, as shown in Figure 7, the melt viscosity increased as the residence time became longer. The thermal stability was inferior to that of the obtained polyamide.

Examples 11 and 12 Polyamides obtained in Examples 1 and 4 100% each
Silane-treated glass fiber with a fiber length of 3 mm and a fiber diameter of 13 μm (trademark of Nittobo Co., Ltd.: C5-)
3PE-476S) was added in the amount shown in Table 1, mixed in a tram blender mixer (manufactured by Shuen Seisakusho), melted and kneaded at a temperature of 300°C in a single-screw extruder with a diameter of 30 mm, and then strands were prepared. was cooled in air and cut to obtain pellets.

The obtained pellets were injection molded (Arburg molding machine, maximum clamping force 35 tons, injection pressure 500 kg/cm'', cylinder temperature 320°C, mold temperature 150°C) to obtain test pieces for various measurements. The measured tensile strength (
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 shrinkage rate (ASTM
D-955) results are shown in Table 1.

Comparative Examples 3 and 4 Polyamides obtained in Examples 1 and 4 each 100
Table 2 shows the results of using the same glass fibers as in Examples 11 and 12, but outside the scope of the present invention, based on parts by weight.

Examples 13 and 14 Polyamides obtained in Examples 1 and 4 100% each
Carbon fibers having an average diameter of 12 μm, a length of 3 mm, and an aspect ratio of 250 (trademark: Toshisha Trading Card) were added in the amount shown in Table 3 based on the weight part, and the same procedure as in Examples 11 and 12 was carried out to prepare the carbon fibers shown in Table 3. The results shown in 3 were obtained.

Comparative Examples 5 and 6 Polyamides obtained in Examples 1 and 4 each 100
120 parts by weight of the same carbon fibers as in Examples 13 and 14 were added to each part by weight.
Extrusion strand formation was attempted in the same manner as in 4, but strand formation was not possible in any case.

Examples 15 and 16 Polyamides obtained in Examples 1 and 4 each 100
Based on weight part, cross-sectional diameter 02μm, average fiber length 20μm
The results shown in Table 4 were obtained in the same manner as in Examples 11 and 12 by adding m potassium titanate fibers (Otsuka Chemicals trademark: Tismo-D) in the amounts shown in Table 4.

Examples 17 and 18 Polyamides obtained in Examples 1 and 4 each 100
Aromatic polyamide fibers with an average fiber length of 3 mm (Dupont Company trademark, Evlar) were added in the amounts shown in Table 5 based on the parts by weight, and the same procedure as in Examples 11 and 12 was carried out to prepare the fibers in Table 5.
The results shown in 5 were obtained.

[Effect of the Invention 1] The present invention provides a novel aromatic polyamide that has excellent processability or thermal stability in addition to the excellent heat resistance inherently inherent in aromatic polyamides. Aromatic polyamide resin compositions have excellent dimensional stability and mechanical strength, and are extremely easy to process, so they are used in electrical and electronic parts, automobile parts, precision mechanical parts, and medical equipment parts, which require these physical properties. It is an extremely useful material used as a base material for spacecraft, etc., and has great industrial effects.

[Brief explanation of the drawing]

FIG. 1 to FIG. 6 show Example 1゜2.4. of the present invention.
It is an example of the infrared absorption spectrum diagram of each polyamide powder obtained by No. 5, 7, and 8. Figure 7 shows the resin residence time in the cylinder of a flow tester at a -11 constant temperature of 300°C and a load of 100 kg in order to compare the thermal stability of each polyamide powder obtained in Example 9 and Comparative Example 2. These are the results of measuring the melt viscosity while changing the viscosity. Figure 7 Procedural amendment (voluntary) February 15, 1991

Claims (1)

[Claims] 1) The following formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, X is a fused polycyclic aromatic group or formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ One or more groups selected from the group consisting of.However, Y is a direct bond, -O-, -S-, -SO_2
-, -CO-, -CH_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and R is an alkyl group with 1 to 4 carbon atoms, an alkoxy group,
or halogen group, phenyl group, a is 0, 1 or 2,
b represents 0 or an integer of 1-4. Also, n is 1 to 10
Represents an integer of 00. ) Aromatic polyamide represented by. 2) 2,2-bis[4-(3-aminophenoxy)phenyl]propane and/or 2,2-bis[4
-(4-aminophenoxy)phenyl]propane and an aromatic dicarboxylic acid dihalide in the presence of a dehydrohalogenating agent in an organic solvent at a reaction temperature of 60°C or lower. The method for producing an aromatic polyamide according to claim 1. 3) 2,2-bis[4-(3-aminophenoxy)phenyl]propane and/or 2,2-bis[ It is characterized by being obtained by polycondensing 4-(4-aminophenoxy)phenyl]propane and an aromatic dicarboxylic acid in the presence of a condensing agent at a reaction temperature of 10 to 150°C in an organic solvent. A method for producing an aromatic polyamide according to claim 1. 4) 2,2-bis[4-(3-aminophenoxy)phenyl]propane and/or 2,2-bis[4] represented by formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼
-(4-aminophenoxy)phenyl]propane and an aromatic dicarboxylic acid dialkylate and/or an aromatic dicarboxylic acid dialylate in an organic solvent at
The method for producing an aromatic polyamide according to claim 1, characterized in that it is obtained by polycondensation at a reaction temperature of 300°C. 5) In the polyamide obtained by reacting diamine and dicarboxylic acid or dicarboxylic acid derivative, the following formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is a fused polycyclic aromatic group or formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼) Two or more types of groups.However, Y is a direct bond, -O-, -S--SO_2-
, -CO-, -CH_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and R is an alkyl group with 1 to 4 carbon atoms, an alkoxy group, or a halogen group , phenyl group, a is 0, 1 or 2, b
represents 0 or an integer from 1 to 4. Also, n is 1 to 100
Represents an integer of 0. ) has a repeating unit represented by 1
The ratio is 0.7 to 1.0 mole per mole, and the amount of the monovalent acid or acid derivative is 0.001 to 1.0 mole per mole of aromatic diamine. A polyamide with good thermal stability. 6) A method for producing a polyamide with good thermal stability according to claim 5. 7) In the polyamide obtained by reacting diamine and dicarboxylic acid or dicarboxylic acid derivative, the following formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is a fused polycyclic aromatic group or formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼) Two or more types of groups.However, Y is a direct bond, -O-, -S-, -SO_2
-, -CO-, -CH_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and R is an alkyl group with 1 to 4 carbon atoms, an alkoxy group,
or halogen group, phenyl group, a is 0, 1 or 2,
b represents 0 or an integer of 1-4. Also, n is 1 to 10
Represents an integer of 00. ) has a repeating unit represented by .7~1.0
The heat obtained by reacting the monovalent amine in a molar ratio and in a ratio of 0.001 to 1.0 mol per 1 mol of aromatic dicarboxylic acid or aromatic dicarboxylic acid derivative. Polyamide with good stability. 8) A method for producing a polyamide with good thermal stability according to claim 7. 9) 100 parts by weight of the polyamide according to claim 1 and/or 5 and/or 7 and 5 to 100 parts by weight of the fibrous reinforcing material.
A polyamide resin composition consisting of parts by weight. 10) The polyamide resin composition according to claim 9, wherein the fibrous reinforcing material is selected from the group consisting of glass fibers, carbon fibers, potassium titanate fibers, and aromatic polyamide fibers.