JP3126443B2 - Haloalkylated polymer compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a haloalkyl group-bound polyetheretherketone and a method for producing the same.

[0002]

2. Description of the Related Art At present, many engineering plastics have been developed and practically used. Although these engineering plastics are characterized respectively, Po Li ether ketone are those excellent very heat resistance, mechanical strength, it is expected wide use in the future.

Since this polyetheretherketone has only concentrated sulfuric acid as a solvent, one effective method is to dissolve it in sulfuric acid to obtain a molded product. The sulfuric acid itself is a polar solvent and a reagent for introducing a sulfonic acid group at the same time. Therefore, a sulfonic acid group can be introduced into polyetheretherketone by dissolving polyetheretherketone in sulfuric acid and heating or leaving it for a long time (Japanese Patent Publication No. 63-51174). It has been clarified that the amount of sulfonic acid group introduced can be controlled by appropriately selecting conditions.

[0004] As described above, it is known that polyether ether ketone introduces a negative charge such as a sulfonic acid group, and can be easily implemented because polyether ether ketone dissolves in sulfuric acid. However, this polyetheretherketone has no solvent other than sulfuric acid to dissolve. That is, if the polyetheretherketone is dissolved in a halogen-based solvent, for example, introduction of a halomethyl group can be carried out in the presence of a Lewis acid, but there is no suitable halogen-based solvent for dissolving the polyetheretherketone. Therefore, a polyetheretherketone into which a functional group other than a sulfonic acid group has been introduced has not been obtained to date.

[0005]

If a reactive group other than a sulfonic acid group can be introduced into polyetheretherketone, a new function can be imparted to this functional resin. In particular, if a reactively active halomethyl group can be introduced, a polyether ether ketone resin can be highly functionalized by starting a crosslinking reaction and binding a compound that reacts with the halomethyl group. From such a viewpoint, various halogen-based solvents have been studied for solvents capable of haloalkylating polyetheretherketone, but no suitable solvent has been found.

[0006]

Means for Solving the Problems The present inventors have studied various methods for introducing a haloalkyl group into polyetheretherketone. As a result, sulfuric acid, which is the only solvent in which polyetheretherketone dissolves, is a Lewis acid, so we considered using sulfuric acid as a solvent for polyetheretherketone and at the same time as a Lewis acid. However, a polyetheretherketone into which a halomethyl group has been introduced under specific conditions has been provided, and the present invention has been provided.

That is, the present invention provides a method for producing a haloalkylated high molecular weight polyetheretherketone, comprising dissolving polyetheretherketone in sulfuric acid and haloalkylating at 20 ° C. or lower.

[0008] The polyetheretherketone of the present invention comprises
The following formula

[0009]

Embedded image

A so-called polyaryletherketone having repeating units (units) having a molecular weight of 1
Any known 000 to 100,000 can be used without any limitation.

In the production method of the present invention, first, polyether ether ketone is generally dissolved in 90% or more, preferably 95% or more of sulfuric acid under stirring, and the introduction of sulfonic acid groups into the polyether ether ketone is prevented. It is important that the sulfuric acid is uniformly dissolved at a temperature of generally 20 ° C. or lower, preferably at a low temperature, in a range where the sulfuric acid does not freeze. Next, a haloalkylation reagent is added thereto to carry out haloalkylation of the polyetheretherketone. In this case, as the haloalkylating reagent to be used, conventionally known haloalkylating reagents such as chloromethyl methyl ether, bromomethyl methyl ether, iodomethyl methyl ether, chloroethyl ethyl ether, chloroethyl methyl ether and the like are not limited at all. The present invention is a reaction in a state where sulfuric acid as a solvent is present in a large excess as a solvent, and since the reaction rate is extremely fast, the haloalkylation is carried out while sufficiently stirring the sulfuric acid solution of polyetheretherketone uniformly. Reagents need to be added. The amount of the haloalkyl group introduced into the polyetheretherketone is appropriately determined by the ratio of the number of moles of the haloalkylating reagent to be added and the number of moles of the unit into which the haloalkyl group of the polyetheretherketone is introduced in the reaction bath. Can be controlled. Although the reaction proceeds very quickly, the reaction time is selected between 10 minutes and 16 hours.

After the reaction, the remaining haloalkylating reagent is removed by a stream of nitrogen, and after removing the harm, sulfuric acid containing a polyetheretherketone derivative having a haloalkyl group introduced thereinto is introduced into a large amount of water to precipitate and precipitate. By washing with water, a haloalkylated polyetheretherketone can be obtained.

In the present invention, the bonding ratio of the haloalkyl group to the polyetheretherketone can be determined by changing the ratio between the polyetheretherketone and the haloalkylating agent in the reaction bath as described above. Although the degree of haloalkylation needs to be changed depending on the purpose, 0.05 to 0.9 can be introduced per unit 1 of polyetheretherketone. This is appropriately selected depending on the purpose of use of the polyetheretherketone into which the haloalkyl group has been introduced.

[0014]

It is known that a haloalkyl group generally decomposes in concentrated sulfuric acid to be converted to benzyl alcohol and forms an ester with sulfuric acid.
Although such a side reaction is considered to have occurred in the present invention, a haloalkyl group is present in the obtained polyetheretherketone, and the sulfur content is extremely low. This is presumed to be because the reaction of the present invention is generally performed at a low temperature of 20 ° C. or less, and the haloalkyl group is stably present despite the presence of a large excess of sulfuric acid. In addition,
The presence of the haloalkyl group can be confirmed by NMR (nuclear magnetic resonance) spectroscopy.

The haloalkylated polyetheretherketone of the present invention can have new functionality due to the presence of a reactive haloalkyl group. Alternatively, a crosslinked structure can be obtained by mixing a haloalkylated polyetheretherketone and a normal polyetheretherketone, molding the mixture, and performing heat treatment. Not only polyetheretherketone but also a crosslinked structure can be formed by mixing with, for example, polysulfone, polyethersulfone, polyimide, polyetherimide, and the like, followed by heat treatment. Further, the heat resistance of the molded article is remarkably improved by forming a crosslinked structure.

Also, a polyetheretherketone having a haloalkyl group bonded thereto is dissolved in sulfuric acid and cast, and the sulfuric acid is sequentially diluted to obtain a remaining film, which is washed with water.
After drying, the film can be subjected to various reactions to obtain a functional film. Also, a sulfuric acid solution is dropped into 80% sulfuric acid to obtain a granular resin, and then diluted sequentially with 40% sulfuric acid and water to obtain a granular resin comprising a polyetheretherketone having a haloalkyl group bonded thereto. It can also be a functional resin that reacts with various reagents that can react with. Alternatively, a polymer using sulfuric acid as a solvent, such as polyetheretherketone or haloalkyl group-free Kevlar (trade name of DuPont) and a polyetheretherketone having haloalkyl group are dissolved in sulfuric acid, and the same operation as above is performed. Then, functional polymers having different amounts of functional groups can be obtained.

[0017]

EXAMPLES The contents of the present invention will be specifically described by the following examples, but the present invention is not limited by the following examples.

Example 1 Polyetheretherketone (trade name VI, manufactured by ICI)
25 parts of CTREX450P) was mixed with 1000 parts of 98% concentrated sulfuric acid, cooled to 4 ° C., stirred and dissolved. A brown, homogeneous, viscous solution resulted. Then, the mixture was cooled to 4 ° C., and chloromethyl methyl ether 50 having a purity of 90% was added.
Part was dropped. Stir for 6 hours while maintaining the temperature at 4 ° C,
When this was poured into a large amount of water, a hard polymer slightly brownish was obtained. Wash this thoroughly with water and adjust the pH of the washing solution.
Washing was conducted while checking for excess sulfuric acid. Next, this was dried under reduced pressure to obtain the polymer of the present invention. Elemental analysis showed that Cl was 25.04% and sulfur was 0.36%. When this was measured by proton NMR, the absorption based on hydrogen in the aromatic ring was observed at 1.8 ppm, and the absorption of hydrogen in the benzyl group was observed at 4.62 ppm.

Example 2 Same polyetheretherketone as used in Example 1 3.
3 parts were dissolved in 490 parts of 95% concentrated sulfuric acid by cooling to 4 ° C. After one hour stirring while maintaining the 4 ° C. by the addition of chloromethyl methyl ether 0.6 parts viscous liquid of brown, N ₂
After removing chloromethyl methyl ether by flowing an air current, the mixture was poured into a large amount of water. The polymer obtained in the same manner as in Example 1 was sufficiently washed and subjected to elemental analysis.
Was 2.86%.

Example 3 As in the previous example, 2.5 parts of polyetheretherketone was dissolved in 100 parts of 95% concentrated sulfuric acid with stirring at 4 ° C. while cooling. After 5 parts of bromomethyl methyl ether was added dropwise to this homogeneous brown solution and stirred for 3 hours, the mixture was passed through a stream of N ₂ as in Example 2 and then poured into a large amount of water to obtain a polymer. Elemental analysis of this Br showed 8.65%.

Example 4 After reacting the chloromethylated polyetheretherketone obtained in Example 1 with the reagents shown in Table 1, elemental analysis and water content when the polymer was equilibrated with pure water = (wet weight−dry weight) ) / Dry weight was measured. The dry weight was indicated by the weight of the resin after drying at 60 ° C. under reduced pressure for 4 hours.

[0022]

[Table 1]

Claims (1)

(57) [Claims] 1. A method for producing a haloalkylated high molecular weight polyetheretherketone, comprising dissolving polyetheretherketone in sulfuric acid and haloalkylating at a temperature of 20 ° C. or lower.