JPS6354430A - Molding of diacetylene group-containing aromatic polyamide - Google Patents

Abstract

PURPOSE:To obtain the title molding having a high strength and a high modulus and being easily surface-treated, by molding a specified diacetylene group- containing aromatic polyamide. CONSTITUTION:An amine (a) of formula I (wherein X and X' are each H, a 1-20C hydrocarbyl group or a carbonyl, sulfonyl or the like bonded to this group and R and R' are each a 1-20C bivalent aromatic hydrocarbyl group) 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 halogen and Z is a 1-20C bivalent hydrocarbyl 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 10min-10hr to obtain a diacetylene group- containing aromatic polyamide having repeating units of formula V. This polyamide is molded into any desired shape.

Description

Detailed Description of the Invention [Technical Field of Application of the Invention] The present invention relates to a molded article of aromatic polyamide containing diacetylene groups, and more specifically to a molded article of aromatic polyamide containing diacetylene groups, and more specifically to a molded article of diacetylene group-containing aromatic polyamide. The present invention relates to a molded article of aromatic polyamide containing acetylene groups.

[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), ) [Problems 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 powders or single crystals of raw material monomers. Therefore, it cannot be obtained as a large molded product, and the polymer itself is often insoluble in water and organic solvents, so the processability after polymerization is extremely poor.

In addition, diacetylene compounds with topochemical polymerizability that have been synthesized and researched so far include HOCH, CmiC-C
The research has been limited to compounds with hydroxyl groups such as cctrzou 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 -N
When the diacetylene compound has a topobond, the intermolecular force due to hydrogen bonding and the reactivity of the nitrogen atom can be utilized, which may strengthen the intermolecular interaction between diacetylene compounds and develop various derivatives, which may lead to the development of topochemical reactions. There are great expectations for its potential and its practical application.

From this point of view, polyamides having diacetylene groups are of great interest, but so far no diacetylene group-containing polyamides exhibiting such topochemical reactivity have been known.

The present inventors have conventionally investigated methods of introducing various groups such as alkyl groups next to diacetylene groups and the properties of the resulting compounds, and in the process, they have been involved in the synthesis of diacetylene group-containing aromatic polyamides. 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 1 to 20 carbon atoms, and 2 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. ) A molded article of diacetylene group-containing aromatic polyamide is provided.

In the present invention, x and x' are each one or two selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbonyl group or sulfonyl group bonded to the hydrocarbon group, and a halogen atom. The above groups or atoms, and examples of hydrocarbon groups having 1 to 20 carbon atoms include CHz,
CtHs,c,n,,C,,H9,CsL+,CJ+
z, CJ+s, C5Lt, C9H14, CIII
H2I, CHz=CI-, CIhCH=CH-, HCC
1HC= and is preferably an unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the above aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group is 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-co- or Y-
It is a group represented by SOz- (Y represents the hydrocarbon group), and examples include cnsc-1PhCHzC-
, CHsSOt-, CzHsSOz-1c:v, soz
-1CJwSO*-1phsot-1PhCHgSOt
-, etc. are preferred.

Examples of the halogen atom include F, C1, Br, and I, preferably (J and Br).

Among these xSx', particularly preferable is X1X'
This is the case when both are hydrogen atoms, and this is because they are excellent in terms of topochemical properties, heat resistance, strength, etc. due to improved cohesive force.

In the present invention, R, R'' represent a divalent aromatic hydrocarbon group having 1 to 20 carbon atoms, and its (:), CC1
+j': ○, C3, LH) and e may be substituted with a halogen atom, cyano group, carboxyl group, amide group, ester group, carbonyl group, ether bond, etc.

Among these RSR', preferable are ortho form and meta form of ○ in terms of topochemical properties, and ○ in terms of moldability.
It is a rose body.

In the present invention, Z is a divalent hydrocarbon having 1 to 20 carbon atoms, and examples thereof include -ct+g
-1-CJa-1-C3H, -1-C, +! , t-2-
C, H,,-1”C111+th-1-CH6)1t6
-1-CiJzt-1-czoo*o-1C1h
C) Is CH, - CH, -CH, - groups, and some of the hydrogen atoms of these Z are halogen atoms, nitro groups, hydroxyl groups, cyano groups, carboxyl groups, amino groups, It may be substituted with an amide group, ester group, carbonyl group, ether bond, etc.

Preferably as Z, −ζ), −
C mountain-1-CsH+h-, -C+ mountain. − is.

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, a sulfonyl group, etc. In the present invention, R1R' and Z of the present invention include X, X'',
As a combination of R, R', Z, (X, X', R
, R', Z) are preferred, but are not limited to ease of synthesis and topochemical properties.

In the present invention, the degree of polymerization of the diacetylene group-containing aromatic polyamide (hereinafter abbreviated as material polyamide), which is the raw material for the molded body of the diacetylene group-containing aromatic polyamide, is an integer of 2 or more and is not particularly limited. However, an integer of 5 or more is preferable, and an integer of 50 or more is preferable in order to provide sufficient moldability and strength.

In the present invention, there is no particular restriction on the weight percent of the raw material polyamide in the molded article, and it may be blended or copolymerized with other monomers or polymers.

Examples of methods for producing the material polyamide include oxidative coupling polymerization using a halogen atom), a carboxylic acid ester (hereinafter referred to as method 1), and an amide metal catalyst (hereinafter referred to as method 2). is given as an example.

In the case of method 1, for example, the amine HNRCmCC=combination 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. The material polyamide can also be synthesized by combining amine HNRC/CCICR'NH with a carboxylic acid halide, carboxylic acid ester, or carboxylic acid. in this case,
An organic solvent may not be used 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, 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 the above method 1, the amount of carboxylic acid halide, carboxylic ester, or carboxylic acid relative to the amine is not particularly limited, but is preferably from 0.1 equivalent to 2 equivalents.

The temperature is 20℃ to 300℃, and the reaction time is 20 minutes to 10 minutes.
It's time.

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 ml11n. Pyridine is preferred as the solvent used in this reaction,
It is also possible to coexist other solvents, and there are no particular restrictions on the reaction temperature and reaction time. Preferably, the reaction temperature may be between -20°C and 100°C, and the reaction time may be in the range of 20 minutes to 12 hours. be.

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 more. 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 confirmed and identified by infrared spectroscopy (hereinafter referred to as IR), laser Raman method, X-ray method, thermal analysis method, and nuclear magnetic resonance method.

The diacetylene group-containing aromatic polyamide molded product of the present invention is obtained by molding the raw material polyamide, and exhibits a high elastic modulus.The value of the developed elastic modulus varies depending on the molding method and conditions. If used, the 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 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.

As the elastic modulus of the molded article of the present invention, flexural modulus or tensile modulus can be applied depending on the shape of the molded article.

The standard method for measuring flexural modulus is 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.

Therefore, 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 151 m or more, a width of 4 fl, a height of 2 cranes, a distance between fulcrums of 10 cranes, a fulcrum tip radius of 2R1, a pressure wedge tip radius of 5R1 test. The measurement was performed at a speed of 5 m/sin. In this case, although the flexural modulus was measured to be slightly smaller than the ASTM method, almost similar values were obtained.

Since the diacetylene bonds 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, pressure, heat, ultraviolet rays, etc. It is effective to apply excitation energy such as , radiation, etc. singly or in combination. These excitation energies can be applied after or simultaneously with imparting the shape.

In particular, as a method for developing a high degree of elasticity, a method of molding under high pressure is preferable, and for example, a pressurizing method such as press molding or isostatic pressing 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., particularly preferably, while improving the elastic modulus in one direction by stretching, and after stretching.
Applying such energy is also effective, and a molded product with improved elastic modulus can be obtained.

〔Effect of the invention〕

The molded article of the aromatic polyamide containing diacetylene groups of 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. Therefore, by crosslinking with heat, pressure, light irradiation, etc., even higher strength and strength can be achieved.
It can have a high elastic modulus. In addition, since the surface energy of the molded article is low due to the presence of amino groups, surface treatment is easy, and hydrophobicization, hydrophilization, doping, etc. are very easy to perform, and secondary high functionality can also be expressed.

Therefore, the molded product of the diacetylene group-containing aromatic polyamide of the present invention can be used for organic conductive materials based on the π-electron conjugated system in the main chain, electronic materials such as 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.

〔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] Add 1ltNQcmiccmiCQNIh to the solution dissolved in
An aqueous IN sodium hydroxide solution containing 2 mol of sodium hydroxide was added, and the mixture was stirred at 0° C. for 30 minutes, and then the precipitated white polymer was isolated using a suction filtration iW. The thus obtained polymer was preformed using a molding apparatus (FIG. 1) at 300 atn for 5 minutes at room temperature. Using a hydrostatic pressure device (Fig. 2), the molded body made in this way was further heated to 6000 atm.
It was treated at 100°C for 60 minutes. The flexural modulus of this molded body after preforming was 3.5 GPa, and the flexural modulus after hydrostatic pressure treatment was 4. I GPa.

[Example 2] CI20C (CHz) instead of Cl0CQCOCAO
Example 1 was repeated except using 4COc it.

In this case, Example 1 was repeated except that the flexural modulus after preforming was 3.40 Pa.

In this case, the flexural modulus after preforming is 3. OGPa, and the flexural modulus after hydrostatic pressure treatment was 4.3 GPa.

[Example 4] 10 g of the polyamide obtained in Example 1 was dissolved in dimethyl sulfoxide to which NaH1, Og was added, 500 mg of propargyl bromide was immediately added, and the mixture was stirred for 30 minutes. After the reaction, the reaction product was poured into 1000 mj+ of water and precipitated. The resulting polymer was isolated by suction filtration. The polymer thus obtained was molded in the same manner as in Example 1.

As a result, the bending elastic modulus after preforming was 3.3 GPa, and the bending elastic modulus after hydrostatic pressure treatment was 4.3 GPa. It was IGPa.

[Example 5] 50% polyamide of Example 1 and 50% 6,6-nylon
Example 1 was repeated except that a mixture consisting of:

In this case, the flexural modulus after preforming was 2.6 GPa, and the flexural modulus after high pressure molding was 3.9 GPa.

[Example 6] The dope obtained by dissolving 5 g of the polyamide of Example 1 in 5 mg of formic acid was cast on a glass plate, and the tensile modulus of the film obtained by washing with water was measured. It showed 3.80Pa in terms of direction.

Example 7 Example 6 was repeated except that the polyamide of Example 2 was used. The film thus obtained is isotropically 3.9
GPa was indicated.

Example 8 Example 6 was repeated except that the polyamide of Example 3 was used. The film thus obtained is isotropically 4.
1 GPa.

Example 9 Example 6 was repeated except that the polyamide of Example 4 was used. The film thus obtained is isotropically 5. Q
GPa was indicated.

[Example 10] Example 6 except that the polyamide mixture of Example 5 was used.
repeated. The film thus obtained is isotropically 4. IGPa was shown.

Example 11 Fibers wet-spun from a 30% m-cresol solution of the polyamide of Example 1 exhibited a modulus of 3.6 GPa.

[Example 12] Example 1 except that the polyamide mixture of Example 5 was used.
I manipulated 1. The fiber thus obtained is 3.5 G
The elastic modulus of Pa is shown.

[Example 13] 0.1 mol and 0.7 part of poly(3,3'-diphenylbutadiine-isophthalamide) obtained by low temperature solution polycondensation method in 3,3'-diaminodiphenylptadiine-methylpyrrolidone was packed in a cylinder of a molding apparatus shown in FIG. 3, and the air in the cylinder was evacuated using a vacuum pump. The molding device was placed on a hydraulic press that had been previously heated to 130° C., and the molding device was preheated for 5 minutes, followed by compression molding at a pressure cuff of 960 kg/cj and a pressing time of 60 minutes. The obtained molded body had a black disc shape with a thickness of about 2 nm and a diameter of 2 Q mm.

The obtained molded body was cut into a rectangular parallelepiped with a height of 14 m, a width of 13 m, and a thickness of 2 m to form a test piece, and the test speed was 0.5 m/w.
A compression test was conducted using an Autograph DSS-500 model (manufactured by Shimadzu Corporation) under the conditions of 1. The compressive strength rate of the molded body was 4.5 GPa, and the strength was 0013 GPa.

[Examples 14, 15, and 16] When the molding conditions of Example 13 were changed in various ways and molding was performed, similar molded bodies were obtained. The mechanical properties of the molded body are shown in Table 1.

Table 1

[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 a molded polymer, and 9.10 is an O-ring. FIG. 2 is a schematic diagram of a hydrostatic pressure device. In the figure, 11 is
A hydraulic pump, 12 a pressure gauge, 13 a high pressure container, 14 a band heater, and 15 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 the inner cylinder, 5゛ is the base, 6′ is the air exhaust pipe, 7゛ is the support rod, 8゛ is the O-ring holder, 9゛ is the mirror plate, 10′ is
11' is above the O-ring, 11' is below the O-ring, and 12' is the molded resin powder.

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 1 to 20 carbon atoms, and Z represents a divalent hydrocarbon group having 1 to 20 carbon atoms. ) A molded article of diacetylene group-containing aromatic polyamide