JPH04252225A - Fluorine-containing aramid block copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title copolymer with low hygroscopicity and low dielectric constant, excellent in heat resistance by etherification of the hydroxyl groups in a specific aramid block copolymer with a fluorine-contg. etherifying agent. CONSTITUTION:A polycondensation is carried out between (A) an aromatic polyamide of formula III (n is 1-30) produced by polycondensation between (1) an aromatic diamine of formula I (Ar is benzene ring-contg. divalent aromatic group) and (2) a hydroxybenzenecarboxylic acid of formula II, (B) a hydrocarbon having carboxyl groups at both the ends of formula IV (R is aliphatic hydrocarbon residue 100-5000 in molecular weight, etc.) and (C) a polybutadiene-acrylonitrile copolymer into an aramid block copolymer with each 2-20 block units of formula IV an formula V mutually connected through amide links. Thence, this aramid block copolymer is etherified with an etherifying agent having 1-22C fluorine-contg. alkyl group, thus giving the objective copolymer highly soluble to solvents.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to a novel fluorine atom-containing aramid block copolymer and a method for producing the same.

0002

BACKGROUND OF THE INVENTION Conventionally, research has been actively conducted on composite materials that create new useful functions by combining a plurality of materials to complement each other's properties. For example, glass fibers, carbon fibers, aramid fibers, and the like are widely used as reinforcing fibers for reinforcing organic polymers, and contribute to improvements in elastic modulus, heat distortion temperature, electrical properties, and the like. Among these, polyamide-aliphatic block copolymers and polyamide-polybutadiene block copolymers are used as heat-resistant elastomers that have excellent heat resistance, impact resistance, solvent resistance, toughness, etc., and are used for modification of various resins. It is attracting attention as a quality material.

0003

[Problems to be Solved by the Invention] However, the polyamide-aliphatic block copolymers and polyamide-polybutadiene block copolymers that have been proposed so far have excellent mechanical properties and heat resistance, but have poor solvent solubility. Its applicability is limited because it has problems such as poor processability and insufficient compatibility with other resins. Furthermore, it has problems of high hygroscopicity and high dielectricity, making it particularly difficult to apply to the field of electronic materials. Therefore, the present invention has been made with the aim of improving these problems. That is, an object of the present invention is to provide a useful new aramid block copolymer that is heat resistant, has low hygroscopicity, low dielectric constant, has high solvent solubility, and is highly processable.

0004

[Means for Solving the Problems] The fluorine-containing aramid block copolymer of the present invention has a block unit represented by the following general formula (I) and a block unit represented by the following general formula (II) each formed by an amide bond. It is characterized by having an intrinsic viscosity of 0.1 to 3.0 dl/g.

(In the formula, R represents a linear or branched aliphatic hydrocarbon residue with a molecular weight of 100 to 5000, a polybutadiene residue, or a butadiene-acrylonitrile copolymer residue, and R1 represents a hydrogen atom or Represents a linear or branched fluorine atom-containing alkyl group having 1 to 22 carbon atoms, and Ar
represents a divalent aromatic group containing a benzene ring which may have a substituent. However, 20% or more of all R1 contained in the fluorine-containing aramid block copolymer is a linear or branched fluorine atom-containing alkyl group having 1 to 22 carbon atoms, and n means an integer of 1 to 30. . )

000
6] In this specification, the intrinsic viscosity means a value measured at 30°C of a dimethylacetamide solution having a resin concentration of 0.5 dl/g.

Various methods can be used to produce the fluorine-containing aramid block copolymer of the present invention, but the following method is preferred in terms of ease of reaction and cost. First, an aromatic diamine represented by the following general formula (III) and H2N-Ar-NH2
(III) (wherein, Ar has the same meaning as above) by condensation polymerization with hydroxybenzenedicarboxylic acid represented by the following general formula (IV),

[0008]

(In the formula, Ar has the same meaning as above, and n means an integer of 1 to 30.) An aliphatic hydrocarbon having carboxyl groups at both ends represented by the following general formula (VI) , polybutadiene, or butadiene-acrylonitrile copolymer to form HOOC-R-COOH.
(VI) (wherein R represents a linear or branched aliphatic hydrocarbon residue, a polybutadiene residue, or a butadiene-acrylonitrile copolymer residue with a molecular weight of 100 to 5000.)

[0010] An aramid block copolymer comprising 2 to 20 block units represented by the following general formula (I') and 2 to 20 block units represented by the following general formula (II) through amide bonds. manufacture,

(In the formula, R, Ar and n have the same meanings as above.) Next, the hydroxyl group of the aramid block copolymer is
Etherification is carried out using an etherification agent having a linear or branched fluorine atom-containing alkyl group having 1 to 22 carbon atoms.

The present invention will be explained in detail below. First, an aromatic diamine represented by the above general formula (III) and a hydroxybenzenedicarboxylic acid represented by the above general formula (IV) are subjected to condensation polymerization to produce a polyamide represented by the above general formula (V).

Specific examples of the aromatic diamine represented by the above general formula (III) include m-phenylene diamine, p-phenylene diamine, metatolylene diamine, 4,4'-diaminodiphenyl ether, 3,3 ´−
Dimethyl-4,4'-diaminodiphenyl ether, 3
, 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4' diaminodiphenyl thioether, 3,3'-dimethyl-4,4'-diaminodiphenyl thioether, 3,3'-diethoxy-4
, 4'-diaminodiphenylthioether, 3,3'-
Diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-
Dimethoxy-4,4'-diaminodiphenylmethane, 2
, 2'-bis(3-aminophenyl)propane, 2,2
'-Bis(4-aminophenyl)propane, 4,4'-
Diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3
'-diaminobiphenyl, p-xylylenediamine, m
-xylylenediamine, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, 3,3'-diamino-4,
4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxybenzophenone, bis(3
-amino-4-hydroxyphenyl) sulfide, bis(4-amino-3-hydroxyphenyl) sulfide,
Examples include bis(3-amino-4-hydroxyphenyl)sulfone and bis(4-amino-3-hydroxyphenyl)sulfone, which can be used alone or in combination.

Further, as the hydroxybenzenedicarboxylic acid represented by the above general formula (IV), for example, 3-hydroxyphthalic acid, 4-hydroxyphthalic acid, 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid,
Examples include, but are not limited to, -hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 3-hydroxyterephthalic acid, and the like. In the present invention, the polycondensation reaction between the aromatic diamine and hydroxybenzenedicarboxylic acid can be carried out by various known methods, including but not limited to, using a phosphite and a pyridine derivative as the condensing agent. It is preferable to carry out the When a phosphite ester and a pyridine derivative are used together as a condensing agent, not only can the reaction be carried out at a relatively low temperature, but also the side reaction with the hydroxyl group of hydroxybenzenedicarboxylic acid shown in (IV) above can be suppressed. There are advantages that can be achieved. As these condensing agents, phosphite esters include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, and tri-m-tolyl phosphite. , di-m-tolyl phosphite, tri-p-tolyl phosphite, di-p-tolyl phosphite, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-phosphite -p-chlorophenyl and the like. In addition, the pyridine derivatives used together with phosphite in the present invention include pyridine, 2-picoline,
3-picoline, 4-picoline, 2,4-lutidine, 2,
Examples include 5-lutidine and 3,5-lutidine.

When the condensation polymerization reaction is carried out in the presence of the above-mentioned condensing agent, a solution polymerization method using a mixed solvent containing a pyridine derivative is employed. The organic solvent used needs to be an inert solvent to both reaction components and the phosphite ester, but it is also desirable to be a good solvent for both reaction components. Typical examples of such organic solvents are amide solvents such as N-methyl-2-pyrrolidone and dimethylacetamide. During the above-described polycondensation reaction, inorganic salts such as lithium chloride and calcium chloride may be added to the reaction system in order to obtain a polymer with a high degree of polymerization. Furthermore, this polycondensation reaction can be easily carried out in the presence of a phosphite condensing agent and a pyridine derivative, particularly in N-methyl-2-pyrrolidone, by heating and stirring under an inert atmosphere such as nitrogen. Can be done.

The amount of the phosphite condensing agent used in these polycondensation reactions is usually equal to or more than the equivalent molar amount to the carboxyl group, but it is not economical to use more than 30 times the molar amount. It's not a good idea to look at it. Further, the amount of the pyridine derivative used here needs to be at least equimolar to the carboxyl group, but in reality it is preferable to use it in large excess, including its role as a reaction solvent. In the present invention, the amount of the mixed solvent containing the pyridine derivative used is preferably such that it contains 5 to 30% by weight of the reaction component. The reaction temperature is usually 60 to 140°C. In addition, the reaction time is greatly influenced by the reaction temperature, but in any case it is good to stir the reaction system until the highest viscosity, which means the highest degree of polymerization, is obtained, and in most cases it is from several minutes to 20 hours. It is. After the completion of the above condensation polymerization reaction, the reaction mixture is poured into a non-solvent such as methanol or hexane to separate the produced polymer, and further by-products and inorganic salts are removed by a reprecipitation method. Polymers can be obtained.

The obtained polyamide represented by the above general formula (V) is then condensed with an aliphatic hydrocarbon having carboxyl groups at both ends, polybutadiene or a butadiene-acrylonitrile copolymer represented by the above general formula (VI). By polymerization, an aramid block copolymer consisting of a block unit represented by the general formula (I') and a block unit represented by the general formula (II) is synthesized.

Examples of the aliphatic hydrocarbon, polybutadiene, and butadiene-acrylonitrile copolymer having carboxyl groups at both ends represented by the general formula (VI) include 1,8-octanedioic acid and 1,10-decane. diacid, 1,18-octadecanedioic acid, 1,20-eicosanedioic acid, hydrogenated polybutadiene with carboxyl groups at both ends (CI-1000 from Nippon Soda Co., Ltd.), polybutadiene with carboxyl groups at both ends (Hycar
CTB) and butadiene with carboxyl groups at both ends.
Acrylonitrile copolymer (Hycar CTBN)
etc., but other dicarboxylic acids can also be used. This polycondensation reaction can be carried out using a phosphite and a pyridine derivative under the same conditions as described above.

Furthermore, the obtained aramid block copolymer consisting of the block unit represented by the general formula (I') and the block unit represented by the general formula (II) is treated with an etherification agent to form phenol. At least 20% of the hydroxyl groups are etherified. Etherification can be carried out, for example, by (a) reaction with a fluorine atom-containing alkyl halide in the presence of sodium hydroxide or potassium hydroxide, or (b) reaction with a di(fluorine atom-containing alkyl halide) in an alkaline solution of the aramid block copolymer. ) Reaction with sulfuric acid, (c) Reaction of the above aramid block copolymer with a fluorine atom-containing alkyl ester of p-toluenesulfonic acid, (d) Reaction of the above aramid block copolymer with a fluorine atom-containing alkyl alcohol under an acid catalyst. Any known method can be used, such as a dehydration reaction with. However, (c) and (
The method d) not only can be carried out under relatively mild conditions, but also is advantageous in terms of cost because the etherifying agent, fluorine atom-containing alkyl alcohol and its p-toluenesulfonic acid ester, are easily available. preferable. Furthermore, a method of using tris(dialkylamino)phosphonium salts as the etherification agent is also convenient and preferred.

Furthermore, in advance, the above general formula (V)
and a fluorine atom-substituted alkylonium salt, and then condensation polymerization with an aliphatic hydrocarbon having carboxyl groups at both ends represented by the above general formula (VI), polybutadiene, or butadiene-acrylonitrile copolymer. It is also possible to synthesize an aramid block copolymer comprising a block unit represented by the general formula (I) of the present invention and a block unit represented by the general formula (II).

The etherification agent used has 1 to 22 carbon atoms.
It has a straight chain or branched alkyl group, and some or all of the hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. Specifically, for example, the above (d)
In the case of the method, 2,2,2-trifluoroethanol, 2,3,3 as the fluorine atom-containing alkyl alcohol
,3,3-pentafluoro-1-2propanol, 1,
1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,4,4,4-hexafluorobutanol, 2,2,3,3,4,4,4-heptafluoro- 1
-butanol, 2,2,3,3,-tetrafluoro-1
-Pentanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 1H,1H,7H-
Dodecafluoro-1-heptanol, 1H,1H-pentadecafluoro-1-octanol, 1H,1H,11
H-eicosafluoro-1-undecanol, 2,2,
Examples include 2,2',2',2'-hexafluorocumyl alcohol. Further, in the case of method (c), the above-mentioned esters of fluorine atom-containing alkyl alcohols and p-toluenesulfonic acid may be used. In addition, materials other than those described above can also be used as long as they do not impair the purpose of the present invention.

[0022] The amount of the fluorine atom-containing alkyl group introduced into the phenolic hydroxyl group can be varied depending on the purpose, but it is preferably 20 mol% or more in order to fully reflect the effect of the introduction. is necessary. Also,
Since the residual phenolic hydroxyl group is highly reactive, it can be reacted with other compounds or other resins, and therefore it can be used to modify the fluorine atom-containing aramid block copolymer itself of the present invention. It can also be used for functionalization, modification of other resins by crosslinking with other resins, or as a composite material.

[0023]

EXAMPLES The fluorine-containing aramid block copolymer of the present invention will be described in more detail below, but the present invention is not limited thereto. Example 1 16.2 g (1
50 mmol), 5-hydroxyisophthalic acid 23.7
A mixed solution of g (130 mmol), 250 ml of pyridine, 62 g (200 mmol) of triphenyl phosphite, and 10.6 g (250 mmol) of lithium chloride was stirred at 100° C. for 4 hours. The obtained polyamide has an intrinsic viscosity of 0.
It had a value of 54 dl/g. Furthermore, add 1 to this solution.
, 4.6 g (20 mmol) of 10-dodecanedioic acid was added thereto and reacted at 100° C. for 5 hours to effect blocking. After cooling, this solution was poured into 3000 ml of methanol, stirred at room temperature for 1 hour, and the precipitated solid was filtered off and dried to synthesize a resin made of a hydroxyl group-containing aramid block copolymer. The molecular weight of this resin was approximately 4,300 in terms of polystyrene. Add 2 g of the above aramid block copolymer to 200 ml of dimethylacetamide under a nitrogen atmosphere.
After dissolving in, 0.90 g (39 mmol) of metallic sodium
, 2,2,3,3,4,4,4-heptafluoro-1-
Butanol, 1.2 g (6 mmol) was added dropwise over 1 hour, reacted at room temperature for 1 hour, and then heated to 100°C.
The reaction was allowed to proceed for 8 hours while stirring. This solution was dropped into a large amount of methanol to precipitate the polymer, and then filtered. After repeated washing three times with large amounts of methanol, hexane, and ether, vacuum drying was performed at 100° C. overnight to obtain the desired resin made of an aramid block copolymer. The intrinsic viscosity value of this resin was 0.96 dl/g. Furthermore, the infrared absorption spectrum of this purified resin was measured using Analect FX616.
0 and corresponds to C=0 of -NHC(=0)-
663 cm-1, 2896 cm corresponding to -CH2-
Absorption was observed at 1300 cm-1 corresponding to -1, -C-F, and it was confirmed that it was the target compound. In addition, as a result of elemental analysis measurement (Carlo Elver 1108 type) of this resin, H: 5.1%, C: 72.5%, 0: 15.6%,
N: 6.7%, which results in 2, 2, 3, 3, 4, 4,
The addition rate of 4-heptafluorobutyl group was found to be about 50%.

Example 2 4.6 g of 1,10-dodecanedioic acid (2
0 mmol) to 6.9 g (2
A resin made of an aramid block copolymer was synthesized in exactly the same manner except that 0 mmol) was used. The intrinsic viscosity value of this resin was 0.91 dl/g. Furthermore, the infrared absorption spectrum of this purified resin was measured using Analect FX.
Measured at 6160, 1665 cm corresponding to C=0 of -NHC(=0)-, 289 corresponding to -CH2-
Absorption was observed at 1302 cm -1 corresponding to 8 cm -1 and -C-F, confirming that it was the target compound. In addition, as a result of elemental analysis measurement of this resin, H: 6.2%, C:
73.7%, 0:14.0%, N:6.1%, which results in an addition rate of 2,2,3,3,4,4,4-heptafluorobutyl group of about 45%. I understand.

Example 3 5-hydroxyisophthalic acid in Example 1 23.7
g (130 mmol) to 24.8 g (136 mmol)
, 4.6 g (20 mmol) of 1,10-dodecanedioic acid
Hydrogenated polybutadiene with carboxyl groups at both ends (
The desired aramid block copolymerized resin was synthesized in exactly the same manner except that 50.2 g (14 mmol) of CI-1000 (number average molecular weight: 3600, manufactured by Nippon Soda Co., Ltd.) was used. In the above case, the polyamide produced as an intermediate had an intrinsic viscosity of 0.53 dl/g. The intrinsic viscosity value of the above resin was 0.65 dl/g. Furthermore, the infrared absorption spectrum of this purified resin was measured using FX6160 manufactured by Analect, and the C of -NHC(=0)- was measured.
= 1661cm-1 corresponding to 0, 2896cm-1 corresponding to -CH2-, 1299c corresponding to -C-F
Absorption was observed at m-1, confirming that it was the target compound. Elemental analysis measurement results: H: 11.6%, C: 81.5%
, 0:4.6%, N:2.2%, which results in 2,2,
It was found that the addition rate of 3,3,4,4,4-heptafluorobutyl group was about 40%.

Example 4 50.2 g (14 mmol) of hydrogenated polybutane diene having carboxyl groups at both ends (CI-1000, number average molecular weight: 3600, manufactured by Nippon Soda Co., Ltd.) in Example 3 was mixed with carboxyl groups at both ends. polybutadiene (Hy
car CTB, number average molecular weight is 3600, Good
A resin made of the desired aramid block copolymer was synthesized in exactly the same manner except that 50.2 g (14 mmol) of the aramid block copolymer (manufactured by Rich, Inc.) was used. The intrinsic viscosity value of this resin is 0
．． It was 70 dl/g. Furthermore, the infrared absorption spectrum of this purified resin was measured using FX6160 manufactured by Analect.
-1664 cm corresponding to C=0 of -NHC (=0)-
2897 cm-1, -C-, corresponding to 1, -CH2-
Absorption was observed at 1297 cm-1 corresponding to F, confirming that it was the desired compound. Further, as a result of elemental analysis measurement of this resin, H: 9.3%, C: 84.6%, 0:4.
3%, N: 1.9%, which results in 2, 2, 3, 3, 4
, 4,4-heptafluorobutyl group addition rate was found to be approximately 62%.

Example 5 50.2 g (14 mmol) of the hydrogenated polybutadiene having carboxyl groups at both ends in Example 3 was mixed with a butadiene-acrylonitrile copolymer (Hycar CTBN, number average molecular weight 3) having carboxyl groups at both ends.
600, the content of acrylonitrile part is 10 mol%,
A resin made of the desired aramid block copolymer was synthesized in exactly the same manner except that 50.2 g (14 mmol) of the aramid block copolymer (manufactured by Goodrich) was used instead. The intrinsic viscosity value of this resin was 0.78 dl/g. Furthermore, the infrared absorption spectrum of this purified resin was measured using Analect FX616.
0 and corresponds to C=0 of -NHC(=0)-
666 cm-1, 2895 cm corresponding to -CH2-
Absorption was observed at 1304 cm-1, which corresponds to -1 and -CF, and it was confirmed that this was the desired compound. In addition, the results of elemental analysis of this resin were H: 8.8%, C: 83.0
%, 0: 4.3%, N: 3.9%, which results in 2,2
, 3,3,4,4,4-heptafluorobutyl group addition rate was found to be about 78%.

Example 6 16.2 g of m-phenylenediamine in Example 1 (
150 mmol) to 31.0 g (150 mmol) of 3,3'-diaminobenzophenone, 2,2,3,3,4
, 1.2 g of 4,4-heptafluoro-1-butanol (
6 mmol) to 1H,1H,7H-dodecafluoro-1
-A desired resin comprising an aramid block copolymer was synthesized in exactly the same manner except that 1.4 g (4 mmol) of heptanol was used instead. In the above case, the polyamide produced as an intermediate had an intrinsic viscosity of 0.45 dl/g. The intrinsic viscosity value of the above resin was 0.92 dl/g. Furthermore, the infrared absorption spectrum of this purified resin was measured using Analect's FX6160, and -NHC (=
0) - 1668 cm-1 corresponding to C=0, -CH2
Absorption was observed at 2899 cm-1 corresponding to - and 1304 cm-1 corresponding to -C-F, confirming that it was the target compound. In addition, as a result of elemental analysis measurement of this resin, H: 4.6%, C: 73.2%, 0: 16.1%, N
:6.2%, and it was found that the addition rate of 1H,1H,7H-dodecafluoroheptyl group was about 46%.

Example 7 5-hydroxyisophthalic acid in Example 6 23.7
g (130 mmol) to 24.8 g (136 mmol)
, 4.6 g (20 mmol) of 1,10-dodecanedioic acid
A resin made of the desired aramid block copolymer was synthesized in exactly the same manner except that 50.2 g (14 mmol) of hydrogenated polybutadiene having carboxyl groups at both ends was used. In this case, the polyamide formed as an intermediate had an intrinsic viscosity of 0.54 dl/g. The intrinsic viscosity value of this resin was 0.58 dl/g. Furthermore,
The infrared absorption spectrum of this purified resin was measured using the F
Measured with
Absorption was observed at 98 cm-1 and 1302 cm-1 corresponding to -CF, confirming that it was the target compound. In addition, as a result of elemental analysis measurement of this resin, H: 10.6%,
C: 80.8%, 0: 6.2%, N: 2.5%, and it was found that the addition rate of 1H,1H,7H-dodecafluoroheptyl group was about 42%.

Example 8 50.2 g (14 mmol) of the hydrogenated polybutadiene having carboxyl groups at both ends in Example 7 was mixed with a butadiene-acrylonitrile copolymer having carboxyl groups at both ends (the content of acrylonitrile moieties was 10 mole%
) A resin made of the desired aramid block copolymer was synthesized in exactly the same manner except that 50.2 g (14 mmol) of the aramid block copolymer was used. The intrinsic viscosity value of this resin is 0.74 dl/
It was g. Furthermore, the infrared absorption spectrum of this purified resin was measured using Analect's FX6160, and -NHC
1660 cm-1, -C corresponding to C=O of (=O)-
Absorption was observed at 2896 cm-1 corresponding to H2- and 1302 cm-1 corresponding to -CF, confirming that it was the desired compound. In addition, as a result of elemental analysis measurement of this resin, H: 8.0%, C: 81.8%, O: 6.0%,
It was found that the addition rate of 1H,1H,7H-dodecafluoroheptyl group was about 69% with N: 4.1%.

Example 9 16.2 g of m-phenylenediamine in Example 2 (
An aramid block copolymer was synthesized in exactly the same manner except that 33.9 g (150 mmol) of 2,2-bis(3-aminophenol)propane was used instead of 150 mmol). In this case, the polyamide formed as an intermediate had an intrinsic viscosity of 0.42 dl/g. Separately, 50 ml of carbon tetrachloride was introduced into a 100 ml three-neck flask equipped with a cooling tube and a dry nitrogen introduction tube, and 3.3 g (20 mmol) of tris(dimethylamino)phosphine was added and stirred. , 3.0 g (20 mmol) of 3,3,3-pentylfluoro-1-propanol was added to react. Furthermore, this reaction product Tris (
To make 2,2,3,3,3-pentylfluorobutoxyphosphonium chloride into a stable salt (dimethylamino)phosphine, an aqueous solution of 4.9 g (30 mmol) of excess ammonium hexafluorophosphite dissolved in 10 ml of water was prepared. In addition to the above reaction system, crystals of tris(dimethylamino)phosphine 2,2,3,3,3-pentylfluorobutoxyphosphonium hexafluorophosphite were obtained in a yield of 47%. 2 g of the aramid block copolymer synthesized above was dissolved in 30 ml of dimethylformamide under a dry nitrogen atmosphere, 2.7 g (6 mmol) of the above phosphonium salt was added, and the mixture was reacted at -20°C for 4 hours. After the reaction, the polymer was precipitated by a conventional method, and then purified to obtain the desired aramid block copolymer resin. The intrinsic viscosity value of this resin is 0.89 dl/
It was g. Furthermore, the infrared absorption spectrum of this purified resin was measured using Analect's FX6160, and -NHC (
1661 cm-1, -CH corresponding to C=O of =O)-
Absorption was observed at 2898 cm-1 corresponding to 2- and 1305 cm-1 corresponding to -CF, confirming that it was the target compound. In addition, as a result of elemental analysis measurement of this resin, H: 6.7%, C: 75.9%, O: 11.6%,
N: 5.7%, and it was found that the addition rate of 2,2,3,3,3-pentylfluoropropylene was about 38%.

Example 10 5-hydroxyisophthalic acid in Example 9 23.7
g (130 mmol) to 24.8 g (136 mmol)
, 6.9 g (20 mmol) of 1,20-eicosandioic acid was replaced with 50.2 g (14 mmol) of a butadiene-acrylonitrile copolymer having carboxyl groups at both ends (the content of the acrylonitrile moiety was 10 mol%). A resin made of the desired aramid block copolymer was synthesized using the same method except for the following. In the above case, the polyamide produced as an intermediate has an intrinsic viscosity of 0.48 dl/
It was g. The intrinsic viscosity value of the above resin is 0.67 dl/
It was g. Furthermore, the infrared absorption spectrum of this purified resin was measured using Analect's FX6160, and -NHC (
=0)-1664 cm-1 corresponding to C=0, -CH
Absorption was observed at 2895 cm-1 corresponding to 2- and 1304 cm-1 corresponding to -CF, confirming that it was the desired compound. In addition, as a result of elemental analysis measurement of this resin, H: 8.5%, C: 82.2%, 0: 5.0%, N
:4.3%, and the addition rate of 1H,1H,7H-dodecafluoroheptyl group was found to be about 82%.

[0033]

[Effects of the Invention] The aramid block copolymer of the present invention, which is etherified with alkyl groups partially or completely substituted with fluorine atoms, does not lose heat resistance compared to conventional aramid block copolymers. It is a highly useful heat-resistant elastomer that can be expected to have a wide range of applications in the field of electronic materials, etc., due to its low hygroscopicity and dielectricity, and improved solvent solubility.

Claims (1)

[Claims] Claim 1: A block unit represented by the following general formula (I) and a block unit represented by the following general formula (II) are each bonded in the range of 2 to 20 through amide bonds, and the intrinsic viscosity value is 0. 1 to 3.0 dl/g. (In the formula, R represents a linear or branched aliphatic hydrocarbon residue with a molecular weight of 100 to 5000, a polybutadiene residue, or a butadiene-acrylonitrile copolymer residue, and R1 is a hydrogen atom or a carbon number of 1 ~22 linear or branched fluorine atom-containing alkyl groups, Ar
represents a divalent aromatic group containing a benzene ring which may have a substituent. However, 20% or more of all R1 contained in the fluorine-containing aramid block copolymer is a linear or branched fluorine atom-containing alkyl group having 1 to 22 carbon atoms, and n means an integer of 1 to 30. . ) [Claim 2] An aromatic diamine represented by the following general formula (III), and H2 N-Ar-NH2
(III) (In the formula, Ar represents a divalent aromatic group containing a benzene ring which may have a substituent.) Polycondensation of hydroxybenzenedicarboxylic acid represented by the following general formula (IV) and the obtained aromatic polyamide represented by the following general formula (V), (wherein, Ar has the same meaning as above, and n means an integer from 1 to 30), and the following general formula ( VI) Condensation polymerization of an aliphatic hydrocarbon having carboxyl groups at both ends, polybutadiene, or butadiene-acrylonitrile copolymer represented by VI) to produce HOOC-R-COOH
(VI) (wherein R is the molecular weight 10
Represents 0 to 5000 linear or branched aliphatic hydrocarbon residues, polybutadiene residues, or butadiene-acrylonitrile copolymer residues. ) The following general formula (I
') and the block unit represented by the following general formula (II) are each linked to 2 by an amide bond.
An aramid block copolymer is produced in which the hydroxyl groups of the aramid block copolymer are bonded in the range of 20 to 20 atoms (wherein R, Ar and n have the same meanings as above).Then, the hydroxyl groups of the aramid block copolymer are 2. The method for producing a fluorine-containing aramid block copolymer according to claim 1, characterized in that the etherification is carried out using an etherifying agent having 1 to 22 linear or branched fluorine atom-containing alkyl groups.