JPH0338296B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field of application of the invention] The present invention relates to a method for molding a diacetylene group-containing polyamide, and more specifically, a diacetylene group-containing polyamide that is particularly easily polymerized and exhibits a high elastic modulus due to the diacetylene group. The present invention relates to a method of molding polyamide. [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 Vol.
Volume 134, page 219 (1970), Journal of Polymer Science Volume B9, page 133 (1971),
Journal of Polymer Science Polymer Physics Edition Volume 12, Page 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. Since many polymers themselves are insoluble in water and organic solvents, their 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 nitride atoms introduced, the electronegativity and cohesive force of the nitrogen atoms can be utilized, and if the nitride 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 and molded products thereof 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 acetylene group-containing polyamide, 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, or two or more types of groups or atoms, Z represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and the number average degree of polymerization is 2 to 20.
It is 250. The present invention provides a method for producing a diacetylene group-containing polyamide molded article, which comprises molding a diacetylene group-containing polyamide having the following properties under hydrostatic 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] Basic,

【formula】

【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 The group hydrocarbon group may be substituted with a halogen atom, a nitro group, a cyano group, a carboxyl group, an amide group, an ester group, a carbonyl group, an ether bond, or the like. 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 preferred are 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, Z represents a divalent hydrocarbon having 1 to 20 carbon atoms, examples of which include -
CH ₂ −, −C ₂ H ₄ −, −C ₃ H ₆ −, −C ₄ H ₈ −, −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 such as [formula] groups, and alicyclic groups,

【formula】

【formula】

【formula】

【formula】 【formula】

【formula】 aromatic groups such as, and

【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 −. In the present invention, the number average degree of polymerization of the polymer is 2
to 250, and preferably 50 or more in order to have sufficient moldability and strength.In the present invention, as a method for producing diacetylene group-containing polyamide, for example, amines are used as raw materials.

Using [formula], 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 using a metal catalyst such as CuCl (hereinafter referred to as method 2). For method 1, e.g. amine

[Formula] and Carbo acid halide

In the combination of [formula], for example, an amine is dissolved in an alkali aqueous solution,
It can be synthesized by dissolving a carboxylic acid halide in an organic solvent that does not mix with water and mixing these two solutions. Also, amine

[Formula] and Carbo acid ester or carboxylic acid

〔Effect of the invention〕

Since the molded product obtained by the present invention has a high elastic modulus, it can be used for electronic materials such as organic conductive materials based on π-electron conjugated systems, high mobility devices, nonlinear optical materials, and solid phase reaction materials. 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 memories. Examples Hereinafter, the present invention will be described with reference to examples in order to further clarify the present invention, 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. Reference example 1

[Formula] 1 mol and 1 mol of HOOC(CH ₂ ) ₈ COOH were dissolved in 30 ml of N-methylpyrrolidone and reacted at 100°C for 12 hours. After the reaction, the reactants are poured into methanol and the precipitated polymer is isolated. The number average degree of polymerization of the obtained polymer was 248. The polymer unitized in this way is packed into a cylinder of a molding machine shown in FIG. 1, and the inside pressure is reduced by a vacuum pump. Subsequently, the molding machine was placed on a hydraulic press, and molding was carried out at a pressure of 20 MPa and a pressing time of 5 hours. The obtained molded body has a length of 15 mm, a width of 4 mm, and a height of 2.
A rectangular parallelepiped of mm is cut out as a test piece, and the distance between the supports is
10mm, fulcrum tip radius 2R, pressure wedge tip radius
The bending elastic modulus measured using an Autograph DSS-500 type CC type bending tester (manufactured by Shimadzu Corporation) under the conditions of 5R and a test speed of 5 mm/min is 6.4 GPa. Similar experiment

Instead of [expression] To,

The elastic modulus obtained by repeating using [Formula] is 5.3 GPa. . This difference in elastic modulus is attributable to the difference in crosslinking density in the molded product due to the difference in reactivity of diacetylene groups. Example 1 The molded article produced in Reference Example 1 was vacuum-sealed with a polyethylene film, placed in a hydrostatic pressure apparatus shown in FIG. 2, and subjected to hydrostatic pressure treatment at 650 MPa at 200° C. for 2 hours. The obtained molded body has a length of 15 mm, a width of 4 mm, and a height of 2.
A rectangular parallelepiped of mm in diameter was cut out, and the flexural modulus of the test piece was measured in the same manner as 12.3 GPa. Similar experiment

Instead of [expression] to

The elastic modulus obtained by repeating using [Formula] is 10.3 GPa. Example 2 Instead of HOOC(CH ₂ ) ₈ COOH in Example 1,

Example 1 was repeated except that the formula was used. (The number average degree of polymerization of the obtained polymer was 5.) In this case, the obtained elastic modulus was 11.5 GPa. Comparative example 1 2 at 650MPa and 200℃ using a press molding machine.
Time molded. The flexural modulus of the obtained molded body is
It was 4.6 GPa. Similar press forming I did it using The flexural modulus of the obtained compact is
It was 4.3 GPa. Also It was subjected to isostatic pressing at 650 MPa and 200°C for 2 hours. The elastic modulus of the obtained molded body was 4.3 GPa.

[Brief explanation of drawings]

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.

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
Z 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 Z has 1 to 20 carbon atoms. 2 up to 20
valence hydrocarbon group, and the number average degree of polymerization is from 2 to
It is 250. ) A method for producing a diacetylene group-containing polyamide molded article, the method comprising molding a diacetylene group-containing polyamide having the following properties under a hydrostatic pressure of 100 MPa or more.