JPH0338295B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of Application of the Invention] The present invention relates to a method for producing a diacetylene group-containing aromatic polyamide molded article, and more specifically, the present invention relates to a method for producing a diacetylene group-containing aromatic polyamide molded article, and more specifically, a diacetylene group-containing aromatic polyamide molded article that has the ability to be easily polymerized by diacetylene groups. The present invention relates to a method of molding aromatic polyamide under ultrahigh pressure. [Prior art] In recent years, the synthesis of single-crystalline polymers using topochemical reactions through solid-state polymerization has attracted attention, and attempts have been made to develop various highly crystalline polymers with high elastic modulus using this method. It is being (For example, "Organic Nonlinear Optical Materials", CMC (1985), Macromolecule Chemistry No. 134
Vol. 219 (1970), Journal of Polymer Science Vol. B9, p. 133 (1971), Journal of Polymer Science Polymer Physics Edition Vol. 12, p. 1511 (1974). ) [Problem to be solved by the invention] However, the polymers of diacetylene compounds that have been synthesized so far have been obtained by photochemically or thermally polymerizing raw material monomer powder or single crystals. In addition, the polymer itself, water, and organic solvent contain many unnecessary substances, so the processability after polymerization is extremely poor. In addition, diacetylene compounds with topochemical polymerizability that have been synthesized and studied so far are
The research has been limited to compounds having a hydroxyl group such as HOCH ₂ C≡C-C≡CCH ₂ OH and derivatives thereof, which has hindered the progress of research. On the other hand, in materials with nitrogen atoms introduced, the electronegativity and cohesive force of the nitrogen atoms can be utilized, and if the nitrogen atoms have -NH- bonds, the intermolecular force due to hydrogen bonds and the reactivity of the nitrogen atoms can be utilized. This method can be used to strengthen intermolecular interactions between diacetylene compounds and to develop various derivatives, and there are great expectations for the potential of topochemical reactions and their practical application. From this point of view, polyamides having diacetylene groups are of great interest, but so far, diacetylene group-containing polyamides exhibiting such topochemical reactivity are hardly known. [Means for Solving the Problem] The present inventors have conventionally investigated methods of introducing various groups such as an alkyl group next to a diacetylene group and the properties of the resulting compounds, but in the process, diacetylene We succeeded in synthesizing an aromatic polyamide containing acetylene groups, and as a result of further research, we arrived at the present invention. That is, the present invention provides, as a repeating unit, (Here, X and X' are hydrogen atoms, and the number of carbon atoms is from 1 to
Represents one or more groups or atoms selected from up to 20 hydrocarbon groups, carbonyl or sulfonyl groups bonded to the hydrocarbon groups, and halogen atoms, and R and R' each have a carbon number of Indicates a divalent aromatic hydrocarbon group from 3 to 20 (but

(excluding [Formula]), Z represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and the number average degree of polymerization is 2 to 250. ) The present invention provides a method for producing a diacetylene group-containing aromatic polyamide molded article, which comprises molding a diacetylene group-containing aromatic polyamide having the following properties under pressure of 100 MPa or more. In the present invention, X and X' are each a hydrogen atom,
One or more groups or atoms selected from a hydrocarbon group having 1 to 20 carbon atoms, a carbonyl group or sulfonyl group bonded to the hydrocarbon group, and a halogen atom, and having 1 to 20 carbon atoms. Hydrocarbon groups include CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ ,
_{C5H11 , C6H13 , C7H15 , C8H17 , C9H19 ,
C10H21} , _CH2 =CH-, _CH3CH =CH-, _HC≡
C-, _HC≡CCH2- ,

fat such as [formula] aliphatic hydrocarbon group,

【formula】

【formula】

【formula】

Alicyclic hydrocarbons such as [formula] basis,

【formula】

Represents an aromatic hydrocarbon group such as [Formula], preferably an unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, and also the above aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic Group hydrocarbon groups include halogen atoms, nitro groups, cyano groups,
It may be substituted with a carboxyl group, amide group, ester group, carbonyl group, ether bond, etc. In addition, as the carbonyl group or sulfonyl group bonded to the hydrocarbon group, when written in the general formula, Y-
A group represented by CO- or Y-SO ₂ - (Y represents the hydrocarbon group), examples of which include:

【formula】 【formula】

【formula】

【formula】

【formula】

[Formula] CH ₃ SO ₂ −, C ₂ H ₅ SO ₂ −, C ₃ H ₇ SO ₂ −, C ₄ H ₉ SO ₂ −,

【formula】

[Formula] etc., preferably

【formula】

[Formula] CH ₃ SO ₂ −,

[Formula] etc. Examples of the halogen atom include F, Cl, Br, and I, preferably Cl and Br. Among these X, X', particularly preferably X,
This is the case when both X′ are hydrogen atoms, and this is because the topochemical property, heat resistance, strength, etc. are excellent due to improved cohesive force. In the present invention, R and R' have from 3 to 3 carbon atoms.
Indicates up to 20 divalent aromatic hydrocarbon groups, examples of which are:

[Formula] (However,

excluding [expression] Ku),

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. are listed,

【formula】 【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

It may be substituted with a halogen atom, a cyano group, a carboxyl group, an amide group, an ester group, a carbonyl group, an ether bond, etc. as shown in the formula. Among these R and R′, preferable ones are from the viewpoint of topochemical properties.

Ortho form of [formula], formability in terms of

It is the para field of [Formula]. In the present invention, Z has a carbon number of 1 to
Divalent hydrocarbons up to 20, _such as _-CH2- , _{-C2H4- , -C3H6- , -C4H8-} , -
C ₅ H ₁₀ −, −C ₈ H ₁₆ −, −C ₁₀ H ₂₀ −, −C ₁₂ H ₂₄ −, −
C ₂₀ H ₄₀ −,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 【formula】

【formula】

【formula】

Aliphatic groups such as [Formula], and fatty cyclic group,

【formula】

【formula】

【formula】

【formula】

【formula】

Aromatic groups such as [Formula], as well as

【formula】

【formula】

【formula】

【formula】

Examples include composite groups of aromatic groups, aliphatic groups, and alicyclic groups such as [Formula], and some of the hydrogen atoms of these Z are halogen atoms, nitro groups, hydroxyl groups, cyano groups, carboxyl groups. may be substituted with a group, an amino group, an amide group, an ester group, a carbonyl group, an ether bond, etc. What is preferable for Z is that it is easier to obtain,

[Formula] −C ₄ H ₈ −, C ₈ H ₁₆ −, C ₁₀ H ₂₀ −. Furthermore, the hydrocarbon groups in R, R', and Z of the present invention may be bonded with other functional groups such as a carbonyl group, an ester group, an amide group, a sulfide bond, an ether bond, an amino group, and a sulfonyl group. R, R', and Z in the present invention include such cases. An example of this is

【formula】

【formula】

【formula】

【formula】

【formula】

Examples include [Formula]. In the present invention, as a combination of X, X', R, R', Z, (X, X', R, R', Z) is (H, H,

【formula】

【formula】

[Formula]) (H, H,

【formula】

[Formula] -C ₄ H ₈ -) (H, H,

【formula】

[Formula] -C ₈ H ₁₆ -) (H, H,

【formula】

[Formula] −C ₄ H ₈ −) (CH ₃ , CH ₃

【formula】

【formula】

[Formula]) (CH ₃ , CH ₃ ,

【formula】

【formula】

[Formula]) (H, CH ₃ ,

【formula】 【formula】

(H, H,

【formula】

【formula】

[Formula]) (H, H,

【formula】

[Formula] -C ₄ H ₈ -), but it goes without saying that the combination is not limited to this example. In the present invention, the number average degree of polymerization of the diacetylene group-containing aromatic polyamide (hereinafter abbreviated as raw material polyamide) is from 2 to 250, preferably 50 or more in order to have sufficient moldability and strength. In the present invention, there is no particular restriction on the weight percentage of the raw material polyamide in the molded article, and it may be blended or copolymerized with other monomers or polymers. For example, as a method for manufacturing polyamide material, amine is used as a raw material.

【formula】 using carboxylic acid halide

[Formula] (A represents a halogen atom), carboxylic acid ester

[Formula] (B represents a hydrocarbon group), or is carboxylic acid

[Formula] and polycondensation method (hereinafter referred to as method 1), amide

An example is a method of oxidative coupling polymerization of [Formula] using a metal catalyst such as CuCl (hereinafter referred to as method 2). For method 1, e.g. amine

[Formula] and carboxylic acid halogen monster

The combination of [Formula] can be synthesized by, for example, dissolving the amine in an alkaline aqueous solution, dissolving the carboxylic acid halide in an organic solvent that does not mix with water, and mixing these two solutions. Also, amine

[Formula] and carboxylic acid halide, carboxylic acid ester, or carboxylic acid

The material polyamide can also be synthesized by polycondensing [Formula] in an organic solvent in a homogeneous system. In this case, the organic solvent may be omitted if uniformity can be obtained by simply mixing the amine and the carboxylic acid halide, carboxylic ester, or carboxylic acid. Next, in the case of method 2, for example, a separately synthesized amide

[Formula] can be synthesized using a metal catalyst such as CuCl, using pyridine as a solvent and blowing oxygen. In the case of method 1 above, the amount of carboxylic acid halide, carboxylic ester, or carboxylic acid relative to the amine is not particularly limited, but preferably
The amount is 0.1 to 2 equivalents. In the case of method 1 above, there are no particular limitations on the type, concentration, and amount of the alkaline aqueous solution used. In the case of method 1 above, there are no particular restrictions on the reaction temperature or reaction time, and preferably the reaction temperature is -
The temperature is 20°C to 300°C, and the reaction time is 20 minutes to 10 hours. In the oxidative coupling polymerization of method 2 above, the number of moles of the metal catalyst used is preferably 0.01 to 1 equivalent relative to the substrate, and the flow rate of oxygen is preferably 10 to 1000 ml/min. Pyridine is preferable as the solvent used in this reaction, and other solvents can also be used together. There are no particular restrictions on the reaction temperature and reaction time, and the reaction temperature is preferably -20°C to 100°C.
reaction times range from 20 minutes to 12 hours. When synthesizing the raw material polyamide, it is extremely important that the raw material has a high degree of purity, and such purity is preferably 98% or higher. General purification methods such as distillation, recrystallization, and sublimation can be used to obtain such raw materials, but it is important to repeat these purification methods to obtain the required purity. The material polyamide and its synthetic intermediates can be analyzed using infrared spectroscopy (hereinafter referred to as IR), laser Raman method,
It can be confirmed and identified using X-ray method, thermal analysis method, and nuclear magnetic resonance method. The molded article obtained by the present invention is made of polyamide material and exhibits a high modulus of elasticity. The value of the elastic modulus developed depends on the molding method and conditions, and if a preferred method is used, an elastic modulus of 4 GPa or more,
In particular, it is easy to exhibit an elastic modulus of 5 GPa or more. The shape of the molded product obtained in the present invention is, for example, plate-like, block-like, or rod-like, and has a shape and size depending on the intended use. For the elastic modulus of the molded article obtained in the present invention, bending elastic modulus or tensile elastic modulus can be applied depending on the shape of the molded article. ASTM-D790-66 can be used as a standard method for measuring the flexural modulus. However, there are cases where it is not always possible to produce a molded object large enough (long enough) to be measured using the ASTM measurement method. Therefore, in the present invention, the following method was used as a method for measuring the flexural modulus of a small molded body. That is, the method for measuring the bending elastic modulus used in the present invention is to use a test piece with a length of 15 mm or more, a width of 4 mm, a height of 2 mm, a distance between fulcrums of 10 mm, a fulcrum tip radius of 2R,
The pressure wedge tip radius was set to 5R and the test speed was set to 5 mm/min. In this case, although the flexural modulus was measured slightly smaller than the ASTM method, almost similar values were obtained. As a method for molding a molded article having an elastic modulus of 4 GPa or more, a method that allows a crosslinking reaction to proceed during molding can be used, such as extrusion molding, injection molding, compression molding, and the like. Since the diacetylene groups of the material polyamide are extremely reactive, it is thought that the crosslinking reaction can proceed by these methods.More preferably, in order to proceed with the crosslinking reaction more actively, it is preferable to use pressure, heat, ultraviolet rays, radiation, etc. It is effective to apply excitation energy of These excitation energies are
It can be applied after or at the same time as the shape is applied. In particular, a method for developing a high elastic modulus is a method of molding under high pressure, and for example, a pressurizing method such as press molding or isostatic pressing can be used. The pressurizing pressure is 100 MPa or more in order to obtain a high elastic modulus of 4 GPa or more in the bulk compact. Preferably
It is 600MPa or more. In addition, molding is possible by applying pressure under atmospheric pressure, but in order to obtain a molded product without voids, the air in the pressurized container and sample voids must be evacuated during pressurization, and the air must be reduced or vacuumed. It is preferable to form the product into a state and press-mold it. The temperature during pressure molding is not particularly limited. Preferably, the temperature range is from room temperature (20°C) to 350°C, particularly from 120 to 200°C. [Effects of the Invention] The molded product obtained by the present invention not only has high strength and high modulus of elasticity due to the cohesive force of the amino groups, but also has diacetylene groups that can be crosslinked by topochemical reaction. Because it is heated,
By crosslinking with light irradiation or the like, higher strength and higher elastic modulus can be imparted. In addition, due to the presence of amino groups, the surface energy of the molded product is low, so surface treatment is easy, making it hydrophobic, hydrophilic,
Doping etc. are very easy to perform, and secondary high functionality can also be expressed. Therefore, the molded product obtained by the present invention can be used as an organic conductive material based on a π-electron conjugated system in the main chain, an electronic material such as a high-mobility element, a nonlinear optical material, or a material that takes advantage of solid phase reactivity. It can be used as a source of a wide variety of high-performance materials such as fingerprint detection materials, hologram sensitive materials, and three-dimensional memory. (Examples) In order to further clarify the present invention, the present invention will be described below with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples. Furthermore, the reagents used in the examples may be purified as necessary, and this is preferable. Example 1

[Formula] In a solution of 2 moles dissolved in 50 ml of chloroform,

[Formula] Add 1N aqueous sodium hydroxide solution containing 2 moles of
After stirring at ℃ for 30 minutes, the precipitated white polymer was isolated by suction filtration. The number average degree of polymerization of the obtained polymer was 245. In this way, the obtained polymer was heated to 30 MPa using a molding device (Fig. 1).
Preforming was carried out indoors for 5 minutes. The molded body thus formed is further processed using a hydrostatic pressure device (Fig. 2).
It was treated at 600 MPa, 60 minutes, and 100°C. The flexural modulus of this molded body after preforming is 3.6 GPa,
The flexural modulus after hydrostatic pressure treatment was 4.1 GPa. Example 2

Example 1 was repeated except that ClOC (CH ₂ ) ₄ COCl was used instead of ClOC (CH 2 ) 4 COCl. The number average degree of polymerization of the obtained polymer was 232. In this case, the flexural modulus after preforming is 3.4GPa
The flexural modulus after hydrostatic pressure treatment was 4.5 GPa. Example 3

instead of [expression] Example 1 was repeated except that . The number average degree of polymerization of the obtained polymer was 5.4. In this case, the flexural modulus after preforming is 3.0GPa
The flexural modulus after hydrostatic pressure treatment was 4.8 GPa. Example 4 10 g of the polyamide obtained in Example 1 is dissolved in dimethyl sulfoxide to which 1.0 g of NaH has been added, 500 mg of propargyl bromide is immediately added, and the mixture is stirred for 30 minutes. After the reaction, the reaction product was poured into 1000 ml of water, and the precipitated polymer was isolated by suction filtration. The number average degree of polymerization of the obtained polymer was 106. The polymer thus obtained was molded in the same manner as in Example 1. As a result, the flexural modulus after preforming is 3.3GPa
The flexural modulus after hydrostatic pressure treatment was 4.1 GPa. Example 5 50% polyamide of Example 1 and 6,6-nylon
Example 1 was repeated except that a mixture consisting of 50% was used. In this case, the flexural modulus after preforming is 2.6GPa
The bending elastic modulus after high-pressure forming was 3.9 GPa.

[Brief explanation of the drawing]

FIG. 1 is a half-cutaway sectional view of the molding device.
In the figure, 1 is a push rod, 2 is a presser metal fitting, 3 is an outer cylinder lid, 4 is an outer cylinder, 5 is an air exhaust pipe, 6 is an inner cylinder, 7 is a receiving plug, 8 is a molded polymer, 9 and 10 are O
It's a ring. FIG. 2 is a schematic diagram of a hydrostatic pressure device. In the figure,
11 is a hydraulic pump, 12 is a pressure gauge, 13 is a high pressure container, 14 is a band heater, and 15 is a high pressure chamber. FIG. 3 is a half-cut sectional view of the molding device.
In the figure, 1' is a push rod, 2' is a presser, 3' is an outer cylinder, 4' is an inner cylinder, 5' is a base, 6' is an air exhaust pipe,
7' is the receiving rod, 8' is the O-ring holder, 9' is the mirror plate, 10' is above the O-ring, 11' is below the O-ring, 1
2' is molded resin powder.

Claims (1)

[Claims] 1. As a repeating unit, (Here, X and X' are hydrogen atoms, and the number of carbon atoms is from 1 to
Represents one or more groups or atoms selected from up to 20 hydrocarbon groups, carbonyl or sulfonyl groups bonded to the hydrocarbon groups, and halogen atoms, and R and R' each have a carbon number of Represents a divalent aromatic hydrocarbon group with a carbon number of 3 to 20 (excluding [formula]), Z represents a divalent hydrocarbon group with a carbon number of 1 to 20, and the number average degree of polymerization is 2.
From 250. 1. A method for producing a diacetylene group-containing aromatic polyamide molded article, which comprises molding a diacetylene group-containing aromatic polyamide having the following properties under a pressure of 100 MPa or more.