JPS6354431A - Molding of diacetylene group-containing 1,3-substituted aromatic polyamide - Google Patents

Abstract

PURPOSE:To obtain the title molding having a high modulus of elasticity and being excellent in heat resistance, strength and moldability, by molding a specified diacetylene group-containing 1,3-substituted aromatic polyamide. CONSTITUTION:An amine (a) of formula I (wherein X and X' are each H, a 1-20C hydrocarbyl or a carbonyl, sulfonyl, or the like bonded to this group and R and R' are each a 1-20C bivalent aromatic hydrocarbon group bonded in positions 1 and 3 to the amide group and the diacetylene group, respectively) is dissolved in an aqueous alkali solution, and the formed solution is mixed with a water-insoluble organic solvent solution of 0.1-2 equivalent of a carboxylic acid halide of formula II (wherein A is a halogen and Z is a 1-20C bivalent hydrocarbol group), a carboxylic ester of formula III (wherein B is a hydrocarbyl group) or a carboxylic acid of formula IV. The mixed solution is reacted at -20-300 deg.C for 20min-10hr to obtain a diacetylene group- containing 1,3-substituted aromatic polyamide having repeating units of formula V (degree of polymerization >=2). This polyamide is molded into a molding having any desired shape and a modulus of elasticity >=6 GPa.

Description

Detailed Description of the Invention [Technical Field of Application of the Invention] The present invention relates to a molded article using a diacetylene group-containing 1,3-substituted aromatic polyamide. In particular, it relates to a molded article using a diacetylene group-containing 1,3-substituted aromatic polyamide that is easily polymerized and exhibits a high elastic modulus.

[Conventional technology]

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 use this technique to develop various highly crystalline polymers having high elastic moduli.

(For example, "Organic nonlinear optical materials", CMC (1
985), Macromolecule Chemistry Vol. 134, p. 219 (1970), Journal of Polymer Science Vol. 89, p. 133 (1971),
Journal of Polymer Science Polymers
Physics Edition Volume 12, Page 1511 (19
74). ) [Problem to be solved by the invention] However, the polymers of diacetylene compounds synthesized so far have been obtained by photochemically or thermally polymerizing raw material monomer powders or single crystals. It cannot be obtained as a molded article, and the polymer itself is often insoluble in water and organic solvents, so its processability after polymerization is extremely poor.

In addition, diacetylene compounds with topochemical polymerizability that have been synthesized and researched so far are HOCH, C=c-c
This research has been limited to compounds with hydroxyl groups such as accHzO'H and their derivatives, which has hindered the progress of research. On the other hand, in materials into which nitrogen atoms are introduced, the electronegativity and cohesive force of nitrogen atoms can be utilized, and the nitrogen atoms are −
When Nil-bonds are present, intermolecular forces due to hydrogen bonds and reactivity of nitrogen atoms can be used to strengthen intermolecular interactions between diacetylene compounds, and development into various derivatives can be considered, leading to topochemical reactions. There are great expectations for its potential and its practical application.

From this point of view, polyamides containing diacetylene groups and molded products thereof are of great interest, but until now, diacetylene group-containing polyamides that exhibit such topochemical reactivity are largely unknown. . - The present inventors have been studying the methods of introducing various groups such as alkyl groups next to diacetylene groups and the properties of the resulting compounds, and in the process succeeded in synthesizing a polyamide containing diacetylene groups. However, as a result of further research, we have arrived at the present invention.

That is, in the present invention, as a repeating unit, (where x and x' are hydrogen atoms and carbon atoms are 1 to 2
0 to 0, a carbonyl group or sulfonyl group bonded to the hydrocarbon group, and one or more groups or atoms selected from halogen atoms, R,
R' represents a divalent aromatic hydrocarbon group having carbon atoms ranging from several months to 20, with the 1st and 3rd positions bonded to an amide group and a diacetylene group, and in the present invention, x and x' are a hydrogen atom and a carbon atom, respectively. One or more groups or atoms selected from a hydrocarbon group having a number of 1 to 20, a carbonyl group or sulfonyl group bonded to the hydrocarbon group, and a halogen atom, and having a carbon number of 1 to 20. As a hydrocarbon group,
CH:l, CtHs, CJ? , C4H9, CsH++
-Cb■Ix % CJ+s % CII
HI? −, C9HI9 sC9°H2 CHz=
CH-, CHzCH=CH-, HC=C-1HC=j, preferably unsaturated aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and the above aliphatic hydrocarbon groups, alicyclic hydrocarbon groups The hydrogen group and aromatic hydrocarbon group may be substituted with a halogen atom, nitro group, cyano group, carboxyl group, amide group, ester group, carbonyl group, ether bond, or the like.

Further, the carbonyl group or sulfonyl group bonded to the hydrocarbon group is represented by the general formula (and y-c.

- or y-so□- (Y represents the hydrocarbon group.

)○ is a group represented by, for example, CH3C-1PhC
HtC-, CH35O□-1CtHsSOz-1C:
1H7SO□-1C4H9SO□-1PhSOz-1P
Preferred examples include hCH2SO□-.

The halogen atom is F% Cl, Brs I, preferably C11Br.

Among these x and x', it is particularly preferable that both X and It is.

In the present invention, R and R" have 1 to 20 carbon atoms, and the 1st and 3rd positions are amide groups and diacetylene. In the present invention, Z is -CH2-1-C18, -1-CJa-
, -C4H11--C5HIO--, -C1lHI&
---CHJzo--I C1li C1l:I CII* CHff C
H3-CHz-CI! -1-CIlz C-CHz-,
Examples include complex groups of -CH2CH2-C-C1lz-, H CH, - CH, - CH□- group groups, and alicyclic groups, and some of the hydrogen atoms of these Z are halogen atoms, Nitro group, hydroxyl group, cyano group, carboxy, ru group, amino group,
It may be substituted with an amide group, ester group, carbonyl group, ether bond, etc.

-〇, -C are preferable as Z due to ease of acquisition.
4-1 early, -CsH+b-, -CH mountain. − is.

In the present invention, although X, X', R, R', and Z are combined, it goes without saying that the combination is not limited to this example.

In the present invention, the degree of polymerization is not particularly limited other than an integer of 2 or more, but is preferably an integer of 50 or more in order to provide sufficient moldability and strength.

As a method for producing a diacetylene group-containing 1,3-substituted aromatic polyamide, which is a raw material for a molded article using the diacetylene group-containing 1,3-substituted aromatic polyamide of the present invention, for example, amine HNRCECC is used as a raw material. =CR'NH
A method of condensing carboxylic acid halogenated
(referred to as method 2) is given as an example.

In the case of method 1, for example, the combination of amine HNRCiaCC can be synthesized by 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. In addition, a diacetylene group-containing 1,3-substituted aromatic polyamide can be synthesized by polycondensing amine HNRCmiCCMiCR"NH with a carboxylic acid ester or with force X. In this case, amine and carboxylic acid If homogeneity can be obtained by simply mixing esters or carboxylic acids, the organic solvent may not be used. This homogeneous polycondensation can also be applied to carboxylic acid halides.

Next, in the case of method 2, synthesis can be carried out using, for example, a separately synthesized amide metal catalyst, using pyridine as a solvent and blowing oxygen into it.

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 is preferably 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 the above method 1, there are no particular restrictions on the reaction temperature and reaction time, and the reaction temperature is preferably from -20°C to 30°C.
The temperature is 0° 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 0.01 to 1 equivalent relative to the substrate, and the flow rate of oxygen is 10 to 1000mj! /min is preferable. Pyridine is preferred as the solvent used in this reaction, and other solvents may also be present. There are no particular restrictions on the reaction temperature and reaction time, and preferably the reaction temperature is between -20°C and 100°C. , reaction time is 2
It ranges from 0 minutes to 12 hours.

When synthesizing this diacetylene group-containing 1,3-substituted aromatic polyamide, it is extremely important that the raw materials have a high degree of purity. It is important to repeat these purification methods.

This diacetylene group-containing 1,3-substituted aromatic polyamide and raw materials for its synthesis were analyzed using infrared spectroscopy (hereinafter referred to as IR), laser Raman method, xH method, thermal analysis method, and nuclear magnetic resonance method. Can be confirmed and identified.

The molded article using the diacetylene group-containing 1,3-substituted aromatic polyamide of the present invention has a diacetylene group-containing 1
．． By molding using 3-substituted polyamide,
It exhibits a high elastic modulus, that is, an elastic modulus of at least 6 GPa or more. The value of the elastic modulus developed depends on the molding method and conditions, and if a preferable method is used, an elastic modulus of 7 GPa or more can be easily achieved.

The shape of the molded product in the present invention is not particularly limited and may be molded into any shape, such as a plate, a block, a rod, a sphere, a fiber, or a film, depending on the purpose. It has a size.

The elastic modulus in the present invention depends on the shape of the molded product, and the bending elastic modulus or tensile elastic modulus can be applied.The measuring method for the bending elastic modulus is the standard method ASTM-D790-
66 can be used. However, the molded product of the present invention may not necessarily be large enough (long enough) to be measured by the ASTM measurement method. For this reason,
In the present invention, the following method was used to measure the flexural modulus of a small molded product.

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 w or more, a width of 4 fi, and a height of 2 fl, with a distance between fulcrums of 10 m, a fulcrum tip radius of 2 R1 (rust tip radius of 5 R, test The measurement was performed at a speed of 5 m/win.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 6 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, film rolling molding, etc. In the diacetylene bond-containing polyether of the present invention, since the diacetylene bond is extremely reactive, it is thought that the crosslinking reaction can proceed by these methods, and more preferably, in order to proceed with the crosslinking reaction more actively. , Pressure, heat, ultraviolet rays, radiation, etc. excitation energy can be used singly or in combination to develop a particularly high degree of elasticity.For example, a method of forming under high pressure is preferable, such as press molding or isostatic pressing. Pressure methods can be used.

The pressurizing pressure is not particularly limited, but is preferably 15 MPa or more, particularly preferably 100 MPa or more. Furthermore, when pressurizing, 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 the sample voids must be evacuated during pressurization, and the pressure must be reduced or vacuumed. It is preferable to perform pressure molding.

The temperature during pressure molding is not particularly limited. Preferably in the range from room temperature (20°C) to 350°C, especially from 120 to 20°C.
It may be within the range of 0°C.

In order to obtain a film-like molded product, it is preferable to apply excitation energy such as pressure, heat, ultraviolet rays, or radiation after or simultaneously with imparting the film shape, and while improving the elastic modulus in one direction by stretching, It is also effective to apply these energies after the molding, and it is possible to obtain a molded product with a further improved modulus of elasticity.

It is also possible to mix inorganic or organic fillers, pigments, ultraviolet absorbers, stabilizers, etc. during molding.

〔Effect of the invention〕

The diacetylene group-containing 1,3-substituted aromatic polyamide of the present invention is produced by introducing aromatic hydrocarbon groups directly bonded to the 1- and 3-positions into the diacetylene group and the amide group, thereby creating a topochemical structure of the diacetylene group. Its greatest feature is that it has a highly enhanced sexual quality. Generally, the topochemical properties of a diacetylene group are greatly influenced by the type of groups adjacent to the diacetylene group, and the bulkier the adjacent groups are, the lower the reactivity is. For this reason, when a diacetylene group-containing polymer is used as a material, it is interesting to introduce rigid aromatic hydrocarbon groups in terms of heat resistance and strength, but the reactivity of the diacetylene group is a disadvantage. . So far, we have reported on diacetylene compounds having an amide group (1974).
Therefore, by introducing an aromatic hydrocarbon group directly bonded to the diacetylene group and the amide group at the 1- and 3-positions, the heat resistance, strength, and moldability are excellent, and the reactivity of the diacetylene group is not impaired. Since it can be easily crosslinked without having to be used as a material, it is possible to provide an extremely useful new material that can exhibit a high modulus of elasticity.

Therefore, the diacetylene group-containing 1.3-11 model aromatic polyamide of the present invention can be used in electronic materials such as punch conductive materials and high-mobility devices based on π-electron conjugated systems, nonlinear optical materials, and solid phase 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 that take advantage of their reactivity.

Furthermore, the diacetylene group-containing 1,3-substituted aromatic polyamide of the present invention having an -N)I- bond utilizes the reactivity of this amino group to create a new type of polydiacetylene that has not been previously known. It is an extremely important intermediate in the synthesis of For example, carboxylic acids, carboxylic acid anhydrides, acid chlorides, sulfonyl chlorides, isocyanates,
Polyamides that react very easily with alkyl halides, epoxies, etc., exhibit properties completely different from the original polyamides, and are useful as highly functional materials.

〔Example〕

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.

[Example 1] 1 mol of HOOC(CHI)scOOH was mixed with 30 mj of N-methylpyrrolidone! and react at 100°C for 12 hours. After the reaction, the reactants are poured into methanol and the precipitated polymer is isolated. The polymer thus isolated is
The mixture is packed into a cylinder of a molding machine shown in FIG. 1, and the pressure inside is reduced using a vacuum pump.

Next, place the molding machine on a hydraulic press and apply pressure of 20M.
Molding was performed under pressure of 5 hours.

A rectangular parallelepiped with a length of 15 fs, a width of 4, and a height of 2 was cut out from the obtained molded product and used as a test piece.The distance between the fulcrums was 10, the radius of the fulcrum tip was 2R1, the radius of the pressure wedge was 5R1, the test speed was 5Trus/win. Under the conditions, Autograph DSS-500 type, C
The bending elastic modulus measured using a C-type bending test device (manufactured by Shimadzu Corporation) is 6.4 GPa.

The elastic modulus obtained upon repetition 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 2] Example 1 was repeated except that HOOC(CH2) 4COOH was used instead of HOOC(CHz) acOOH. In this case, the elastic modulus obtained is 6.3 GPa.

[Example 3] In Example 1, HOOC(CHz) acOOl(
Instead of, I did. In this case, the obtained elastic modulus is 7.
IGPa.

[Example 4] In this case, the obtained elastic modulus is 6.8 GPa.

[Example 5] The molded product produced in Example 1 was vacuum-sealed with a polyethylene film, placed in the hydrostatic pressure device shown in Figure 2, and heated to 650M.
Hydrostatic pressure treatment of Pa was performed for 2 hours.

The resulting molded product has a length of 15 fins, a width of 4 m, and a height of 21 m.
A rectangular parallelepiped was cut out, and the bending elastic modulus of the test piece was measured in the same manner as 12.3CPa.

The elastic modulus obtained upon return is 10.3 GPa.

[Example 6] In Example 5, HOOC (CHz) 5cOOHO
Instead, I did. In this case, the obtained elastic modulus is 11.5
It is GPa.

[Brief explanation of the drawing]

FIG. 1 is a half-cutaway sectional view of the molding device. In the figure, 1 is the push rod, 2 is the presser metal fitting, 3 is the lid of the outer cylinder, 4 is the outer cylinder, 5 is the air exhaust pipe, 6 is the inner cylinder, 7 is the plug for the receiver,
8 is molded polymer, 9.10 is rolling. FIG. 2 is a schematic diagram of a hydrostatic pressure device. In FIG. 0, 11 is a
A hydraulic pump, 12 a pressure gauge, 13 a high pressure container, 14 a band heater, and 15 a high pressure chamber.

Claims (1)

[Claims] As repeating units, there are ▲mathematical formulas, chemical formulas, tables, etc.▼ (Here, X and X' are hydrogen atoms, and the number of carbon atoms is 1 to 20.
R, R
' represents a divalent aromatic hydrocarbon group having from 1 to 20 carbon atoms and whose 1st and 3rd positions are bonded to an amide group and a diacetylene group, and Z represents a divalent aromatic hydrocarbon group having from 1 to 20 carbon atoms. represents a hydrocarbon group, and the degree of polymerization represents an integer of 2 or more. ) A molded article having an elastic modulus of 6 GPa or more using a diacetylene group-containing 1,3-substituted aromatic polyamide