JP2943233B2 - Method for producing fluorine-containing polyamide - Google Patents

Description

The present invention relates to a novel method for producing a fluorine-containing polyamide.

[Conventional technology]

Conventionally, polyamide has high strength, high elastic modulus, heat resistance,
As an excellent material having flame retardancy, it is applied to fibers, molded products, composite materials, coating materials and the like.

In addition, fluorine-containing polymers make use of unique properties such as excellent heat resistance, chemical resistance, water / oil repellency, and non-adhesiveness.
As a highly functional polymer, its application is widespread.

[Problems to be solved by the invention]

However, in recent years, there has been a strong demand for high functionality such as improvement in moisture absorption resistance of polyamides, and conventional polyamides have not sufficiently satisfied this demand.

Accordingly, the present invention provides a novel method for producing a fluorine-containing polyamide, which has the excellent properties of a fluorine-containing polymer and a polyamide.

[Means for solving the problem]

The present invention relates to a compound represented by the general formula (I): [However, Rf in the formula, -C _n F _2n-1 (where, n represents 6-12
Which contains one double bond, may be branched, and the hydrogen of the benzene nucleus may be substituted with a lower alkyl group, a lower alkoxy group or a halogen. An acid component containing an aromatic dicarboxylic acid or an amide-forming derivative thereof represented by the general formula (II): (Wherein, X represents a divalent organic group and R represents hydrogen or a trialkylsilyl group). The present invention relates to a method for producing a fluorine-containing polyamide, characterized by reacting the diamine.

In the present invention, an aromatic dicarboxylic acid represented by the general formula (I) or an amide-forming derivative thereof is used as an acid component, a diamine represented by the general formula (II) is used as an amine component, and these are subjected to a condensation reaction. As the acid component, a dicarboxylic acid reactive with the diamine or an amide-forming derivative thereof may be used in addition to the aromatic dicarboxylic acid or the amide-forming derivative thereof.

Examples of the aromatic dicarboxylic acid represented by the general formula (I) include 5- (perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid,
-(Perfluorononenyloxy) terephthalic acid, 4-
Methyl-5- (perfluorononenyloxy) isophthalic acid, 4-methoxy-5- (porfluorononenyloxy) isophthalic acid, 2,4,6-trifluoro-5- (perfluorononenyloxy) isophthalic acid , 4-chloro-
5- (perfluorononenyloxy) isophthalic acid, 4
-Bromo-5- (perfluorononenyloxy) isophthalic acid, 4-methyl-5- (perfluorononenyloxy) phthalic acid, 4-methoxy-5- (perfluorononenyl) phthalic acid, 3,4, 6-trifluoro-5- (perfluorononenyloxy) phthalic acid, 4-chloro-5
(Perfluorononenyloxy) phthalic acid, 4-bromo-5- (perfluorononenyloxy) phthalic acid, 2-
Methyl-5- (perfluorononenyloxy) terephthalic acid, 4-methoxy-5- (perfluorononenyloxy) terephthalic acid, 2,3,6-trifluoro-5- (perfluorononenyloxy) terephthalic acid , 2-chloro-
5- (perfluorononenyloxy) terephthalic acid,-
Bromo-5- (perfluorononenyloxy) terephthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) phthalic acid, 2- (perfluorohexenyloxy) terephthalic acid, 4-methyl -5- (perfluorohexenyloxy) isophthalic acid, 4-methoxy-5- (perfluorohexenyloxy) isophthalic acid, 2,4,6-trifluoro-5- (perfluorohexenyloxy) isophthalic acid, 4-chloro -5- (perfluorohexenyloxy) isophthalic acid, 4-bromo-5- (perfluorohexenyloxy) isophthalic acid, 4-methyl-5- (perfluorohexenyloxy) phthalic acid, 4-methoxy-5- (per Fluorohexenyloxy) phthalic acid, 3,
4,6-trifluoro-5- (perfluorohexenyloxy) phthalic acid, 4-chloro-5- (perfluorohexenyloxy) phthalic acid, 4-bromo-5- (perfluorohexenyloxy) phthalic acid, 2- Methyl-5
(Perfluorohexenyloxy) terephthalic acid, 4-
Methoxy-5- (perfluorohexenyloxy) terephthalic acid, 2,3,6-trifluoro-5- (perfluorohexenyloxy) terephthalic acid, 2-chloro5- (perfluorohexenyloxy) terephthalic acid, 2-bromo -5- (perfluorohexenyloxy) terephthalic acid and the like.

The perfluorononenyloxyisophthalic acid and perfluorohexenyloxyisophthalic acid are, for example,
According to the method disclosed in JP-A-60-51146, a trimer or dimer of hexafluoropropene is reacted with hydroxyisophthalic acid in an aprotic polar solvent at room temperature or lower in the presence of a base catalyst. Can be manufactured.

Examples of the perfluorononenyl group include, for example, those represented by the formula (A) And the perfluorohexenyl group includes, for example, a compound represented by the formula (B) There is a group.

In the above method, it is also possible to prepare other dicarboxylic acids using oligomers other than trimers and dimers of hexafluoropropene and oligomers of other fluoroalkenes.

The aromatic dicarboxylic acid represented by the above general formula (I) can be prepared, for example, according to the method described in JP-A-50-121243, such as diphenyl ester and dibenzyl ester of hydroxy-dicarboxybenzene. Of an ester of the above with a fluoroalkene oligomer such as fluoropropene trimer and tetrafluoroethylene pentamer in the presence of a proton acceptor in an aprotic organic solvent at or near room temperature in the presence of a base catalyst at or below room temperature After the reaction, the reaction product is isolated, and the reaction product is hydrolyzed in the presence of a basic compound such as sodium hydroxide, potassium hydroxide or the like, and is then appropriately treated with an acid such as an operation to produce the reaction product. Can be. The reaction product and the final product may be washed,
It is purified by means such as recrystallization.

The amide-forming derivative of the aromatic dicarboxylic acid is
A derivative capable of forming an amide bond by reacting with the diamine represented by the general formula (II), such as an acid halide such as dichloride or dibromide of the aromatic dicarboxylic acid, or a dimethyl ester or diethyl ester of the acid. Dialkyl esters and acid anhydrides of the acids.

The above dichloride can be obtained in high yield, for example, by reacting perfluoroalkenyloxyisophthalic acid with thionyl chloride.

The above dialkyl esters such as dimethyl ester and diethyl ester can be obtained by reacting an alcohol such as methanol and ethanol with perfluoroalkenyloxyisophthalic acid in the presence of an acid.

The dicarboxylic acid or the amide-forming derivative thereof which may be used in combination with the aromatic dicarboxylic acid or the amide-forming derivative thereof includes a compound represented by the general formula (III): [Wherein, Z is (Where Rf is a divalent organic group other than the same as in the general formula (I))], and Z in the general formula (III) is an aromatic ring Dicarboxylic acid which is a divalent organic group containing amide or an amide-forming derivative thereof is preferable in view of heat resistance of the obtained polyamide.

As the divalent organic group containing an aromatic ring, a compound represented by the general formula (a) A group represented by the general formula (b) (Where Z ′ is a bond —O—, —S—, —SO ₂ —, A group represented by the general formula (c) (Where Z 'is the same as above, and two Z's
May be the same or different), a group represented by the general formula (d) (Where Z 'is the same as above and three Z's
May be the same or different), and these groups may be appropriately substituted with a lower alkyl group, a lower alkoxy group, or a halogen such as chlorine, bromine, or fluorine. .

Examples of the dicarboxylic acid represented by the general formula (III) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc., and phthalic acid. , Isophthalic acid, terephthalic acid, 3,3'-dicarboxylic diphenyl ether, 3,4'-dicarboxylic diphenyl ether,
3,4'-dicarboxyl diphenyl ether, 3,3'-dicarboxyl diphenyl methane, 3,4'-dicarboxyl diphenyl methane, 4,4'-dicarboxyl diphenyl methane, 3,3'-di Carboxyldiphenyldifluoromethane, 3,4'-dicarboxyldiphenylolomethane, 4,4'-dicarboxyldiphenyldifluoromethane, 3,3'-dicarboxyldiphenylsulfone, 3,
4'-dicarboxyldiphenylsulfone, 4,4'-dicarboxyldiphenylsulfone, 3,3'-dicarboxyldiphenylsulfide, 3,4'-dicarboxyldiphenylsulfide, 4,4 ' -Dicarboxylic diphenyl sulfide, 3,3'-dicarboxylic diphenyl ketone, 3,4'-dicarboxylic diphenyl ketone, 4,4'-
Dicarboxylic diphenyl ketone, 2,2- (3-carboxylphenyl) propane, 2,2- (3,4'-dicarboxyldiphenyl) propane, 2,2-bis (4-carboxylphenyl) propane, 2,2-bis (3-carboxylphenyl) hexafluoropropane, 2,2- (3,4-dicarboxyldiphenyl) hexafluoropropane, 2,
2-bis (4-carboxylphenyl) hexafluoropropane, 1,3-bis (3-carboxylphenyl) benzene, 1,4-bis (3-carboxylphenoxy) benzene, 1,4-bis (4 -Carboxylphenoxy) benzene, 3,3 '-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 3,4'-(1,4-phenylenebis (1-methylethylidene)) bisbenzo Acid, 4,4 '
-(1,4-phenylenebis (1-methylethylene))
Bisbenzoic acid, 2,2'-bis (4-3-carboxylphenoxy) phenyl) propane, 2,2-bis (4- (4
-Carboxylphenoxy) phenyl) propane, 2,2
-Bis (4- (3-carboxylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4-carboxylphenoxy) phenyl) hexafluoropropane, bis (4- (3-carboxylphenoxy) phenyl Phenyl) sulfide, bis (4- (4-carboxylphenoxy) phenyl) sulfide, bis (4- (3-carboxylphenoxy) phenyl) sulfone, bis (4-
There are aromatic dicarboxylic acids such as (4-carboxylphenoxy) phenyl) sulfone.

Examples of the amide-forming derivative of the dicarboxylic acid represented by the general formula (III) include acid halides of the dicarboxylic acid such as dichloride and dibromide, and dialkyl esters of the dicarboxylic acid such as dimethyl ester and diethyl ester.

As the acid component in the present invention, perfluoroalkenyloxyisophthalic acid represented by the general formula (I) or an amide-forming derivative thereof is preferably used in an amount of 1 to 100 mol%, more preferably 10 to 100 mol%. Mol%, particularly preferably 20 to 100 mol%. If the amount of such an acid component is too small, the obtained polyamide tends to have low moisture absorption resistance.

Among the diamines represented by the general formula (II), trialkylsilylated diamines wherein R is a trialkylsilyl group are described in Macromolecules No. 21;
Volume, p. 547 (1988), and can be adjusted according to the method for producing N, N'-bis (trimethylsilyl) bis (4-aminophenyl) ether as shown below. For example, N, N'-bis (trialkylsilyl) bis ((4-aminophenyl) ether can be obtained by reacting a trialkylsilyl chloride with a benzene solution of bis (4-aminophenyl) ether in the presence of triethylamine. .

As the diamine represented by the general formula (II), X in the general formula (II) is a divalent organic group containing an aromatic ring.
It is preferable in terms of heat resistance of the obtained polyamide. In order to obtain a polyamide having a higher molecular weight, it is preferable to use a trialkylsilylated diamine.

Examples of the above-mentioned aromatic-containing divalent organic group include groups represented by the above-mentioned general formulas (a), (b), (c), and (d). Represents a lower alkyl group, a lower alkoxy group, chlorine, bromine,
It may be substituted with halogen such as fluorine.

Examples of the diamine represented by the general formula (II) include:
2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9 -Diaminononane, 1,10-diaminodecane,
Aliphatic diamines such as 1,11-diaminoundecane and 1,12-diaminododecane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,
3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,
3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone ,
4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,
3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,
2'-bis (3-aminophenyl) propane, 2-2 '
-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4 '
-Diaminodiphenyl) hexafluoropropane, 2,2
-Bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4
-Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4'-(1,4 -Phenylenebis (1-methylethylidene)) bisaniline, 4,4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane,
2,2-bis (4- (4-aminophenoxy) phenyl)
Propane, 2,2-bis (4- (3-aminophenoxy)
Phenyl) hexafluoropropane, 2,2-bis (4-
(4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy)
Aromatic diamines such as phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, and bis (4- (4-aminophenoxy) phenyl) sulfone; and N-trialkylsilylated diamines of these diamines. Can be.

Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a tripropylsilyl group.

The condensation reaction between the acid component and the amine component can be carried out in an aprotic organic solvent in the presence or absence of a trapping agent for hydrochloric acid, an activator or the like.

In this case, the acid component and the amine component are preferably used in an equimolar or almost equimolar manner, and the order of adding each component is arbitrary.

Specific examples of the aprotic organic solvent include amide solvents such as dimethylacetamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, benzene, toluene, anisole, nitrobenzene, benzonitrile. And the like, aromatic solvents such as dibutyl ether, tetrahydrofuran, dioxane, di (methoxyethyl) ether and the like, and halogenated hydrocarbon solvents such as chlorophorom and the like. Among these organic solvents, dimethylacetamide and N-methyl-2-pyrrolidone provide good results for the purpose of obtaining a polyamide having a high degree of polymerization.

The above-mentioned trapping agent for hydrochloric acid is used to neutralize hydrochloric acid generated in the condensation reaction, and it is preferable to use a base such as pyridine, triethylamine, dimethylaniline and the like.

The activator is used for activating an acid component, and includes dicyclohexylcarbodiimide, polyphosphoric acid,
It is preferable to use imidazole or the like.

As a more specific method for producing the polyamide according to the present invention, for example, an ordinary low-temperature solution polycondensation method, an interfacial polycondensation method, a direct polycondensation method and the like can be used. Among these, the low-temperature solution polycondensation method involves dissolving an amine component and, if necessary, a trapping agent in an aprotic organic solvent and then dissolving the solution at about -50 to + 80 ° C, preferably at -20 to + 50 ° C. While stirring, an acid halide such as diacid chloride or diacid bromide as an acid component is added at once or gradually in the form of a powder or a solution in which the acid halide is dissolved in an aprotic organic solvent to cause a reaction. The reaction occurs immediately and the viscosity of the reaction system increases. The stirring is usually continued for 1 to 24 hours. The reaction product after the reaction can be used as a stock solution for molding. Further, the polymer can be isolated by treating with methanol, water, or the like.

The interfacial polycondensation method is performed by dissolving an acid halide such as diacid chloride or diacid bromide as an acid component and an amine component in a solvent that is not mixed with each other. For example, when diacid chloride is dissolved in carbon tetrachloride, chloroform or the like, while an amine component is dissolved in an aqueous alkali solution and added to a solution of an acid halide, condensation occurs immediately at the interface layer to obtain a polymer.

Immediately after the polycondensation method, a dicarboxylic acid as an acid component and an amine component are dissolved in an organic solvent, and dicyclohexylcarbodiimide, polyphosphoric acid, imidazole or the like is added as an activator.

The fluorine-containing polyamide produced according to the present invention is useful as a coating agent and can be formed into a film by a conventionally known solution casting method or the like.

The fluorine-containing polyamide produced according to the present invention is dissolved in dimethylacetamide (DMAc) at a concentration of 0.1 g / dl,
Reduced viscosity measured at 0 ° C is 0.01 dl / g or more, especially 0.04 dl / g
It is preferably at least 0.1 dl / g when producing a film.

The fluorine-containing aromatic polyamide produced according to the present invention exhibits excellent water repellency. For this purpose, the content of fluorine based on Rf in the general formula (I) is 10% by weight or more,
In particular, it is preferably adjusted to be 15% by weight or more.

The polyamide produced according to the present invention has the general formula (IV) Wherein Rf is equal to the general formula (I), hydrogen of the benzene nucleus may be substituted with a lower alkyl group, a lower alkoxy group or a halogen, and X is equal to the general formula (II). Containing the structural unit represented by the general formula (V) [Wherein, Z is equal to the general formula (III) and X is equal to the general formula (IV)].

Such a constituent unit is specified by specifying a raw material. When two or more types of acid components or two or more types of amine components are used as raw materials, there are two or more types of specified structural units. In this case, in the present invention, two or more types of structural units are linear. It may be a random copolymer arranged randomly or a block copolymer arranged linearly and regularly, and the arrangement may be arbitrary. Such an arrangement is adjusted according to the selected starting materials, reaction conditions, order of addition, and the like.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, the present invention,
The embodiment is not particularly limited.

Example 1 In a reaction vessel equipped with a stirring device, 0.540 g (5.00 mmol) of p-phenylenediamine as an amine component, 0.948 g (12.0 mmol) of pyridine, and dimethylacetamide (hereinafter DM)
30.0 g) and cooled to 5 ° C on an ice-water bath.
325 g (5.00 mmol) of 5- (perfluorononenyloxy) isophthalic acid dichloride as an acid component was added to the above solution while stirring. After stirring for 5 hours, the reaction solution was added to a large amount of methanol, and the precipitate was filtered and washed with methanol several times to obtain 3.34 g of a solid white polyamide (1).

Table 1 shows the yield and reduced viscosity of polyamide (1), and Table 3 shows the physical properties of polyamide (1).

Example 2-15 According to the method of Example 1, the diacid chloride component was added to 5
A polymer was synthesized by immobilization on-(perfluorononenyloxy) isophthalic acid dichloride and variously changing the amine component. Table 1 shows the types of the amine components and the yields and reduced viscosities of the obtained polyamides (2) to (15).
Table 3 shows the substances of the polymer amide.

Example 16 N, N'-bis (trimethylsilyl) bis (4-aminophenyl) ether was placed in a reaction vessel equipped with a stirring device.
1.03 g (3.00 mmol), pyridine 0.474 g (6.00 mmol), DMA
c6 ml was added and cooled to 5 ° C. on an ice-water bath. 1.95 g (3.00 mmol) of 5- (perfluorononenyloxy) isophthalic acid chloride (hereinafter abbreviated as PFIP) was added to the above solution while stirring. After 5 hours of stirring,
The reaction solution was added to a large amount of methanol, and the precipitate was filtered and washed several times with methanol to obtain 2.16 g of a solid white polyamide (16).

Table 2 shows the yield and reduced viscosity of polyamide (16), and Table 3 shows the physical properties of polyamide (16).

Examples 7-19 According to the method of Example 16, the amino component was immobilized on N, N'-bis (trimethylsilyl) bis (4-aminophenyl) ether, and PFIP and isophthalic acid dichloride (hereinafter IP) were used as the acid components. ) Was synthesized using the above mixture. Table 2 shows the molar amounts of PFIP charged and the yields and reduced viscosities of the obtained polyamides (17) to (19), and Table 3 shows the physical properties of the polyamides (17) to (19).

Comparative Example 1 N, N'-bis (trimethylsilyl) bis (4-aminophenyl) ether was placed in a reaction vessel equipped with a stirring device.
1.03 g (3.00 mmol), pyridine 0.474 g (6.0 mmol), DMAc
6 ml was put and cooled to 5 ° C. on an ice water bath. IP0.609g (3.0
0 mmol) was added to the solution with stirring. After stirring for 5 hours, the reaction solution was added to a large amount of methanol, and the precipitate was filtered and washed with methanol several times to obtain 0.992 g of a solid white polyamide (20).

Table 2 shows the yield and reduced viscosity of polyamide (20), and Table 3 shows the physical properties of polyamide (20).

The infrared absorption spectra of the polyamides obtained in Example 9, Example 13 and Example 16 are shown in FIGS. 1, 2 and 3, respectively.

The 5- (perfluorononenyloxy) isophthalic acid dichloride used in the examples was Which is obtained by adding 10 mol of thionyl chloride at 80 ° C. to 1 mol of 5- (perfluorononenyloxy) isophthalic acid having a group of the above formula (A) as a perfluorononenyl group. After reacting for 12 hours, the remaining thionyl chloride was distilled off, and then obtained by distillation.
The boiling point of the obtained compound was 114 ° C. and (0.3 mmHg).

〔The invention's effect〕

According to the method of the first aspect, a novel fluorine-containing polyamide having excellent moisture absorption resistance (water repellency and water absorption resistance), particularly excellent water repellency, can be obtained.

[Brief description of the drawings]

1 is an infrared absorption spectrum of the polyamide (9) obtained in Example 9, FIG. 2 is an infrared absorption spectrum of the polyamide (13) obtained in Example 13, and FIG. 3 shows an infrared absorption spectrum of the polyamide (16) obtained in (1).

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 69/00-69/50 C08F 299/02 CA (STN)

Claims (1)

(57) [Claims] 1. The compound of the general formula (I) [However, Rf in the formula, -C _n F _2n-1 (where, n represents 6-12
Which contains one double bond, may be branched, and the hydrogen of the benzene nucleus may be substituted with a lower alkyl group, a lower alkoxy group or a halogen. An acid component containing an aromatic dicarboxylic acid or an amide-forming derivative thereof represented by the general formula (II): (Wherein, X represents a divalent organic group and R represents hydrogen or a trialkylsilyl group). A process for producing a fluorine-containing polyamide, comprising reacting a diamine represented by the following formula: