JPS63145337A - Molding of double bond-containing diacetylene amide oligomer and polymer - Google Patents

Abstract

PURPOSE:To obtain a molding a remarkably improved modulus and good heat resistance, by molding an amide oligomer and its polymer each of which contains two kinds of highly reactive crosslinking groups such as double bonds and diacetylene groups in a high density. CONSTITUTION:This molding is prepared by using a double bond-containing diacetylene amide oligomer and its polymer each formed by linking structural units of at least one diacetylene hydrocarbon of formula I or II with structural units of at least one carbon-carbon double bond-containing diamide through X<1> and X<2>. In formulas I-III, R is H or a monovalent organic group, R<1>, R<2> and R<3> are each a bivalent organic group, R<4> is a carbon-carbon double bond- containing bivalent organic group, and X<1> and X<2> are amide groups. It is preferable that the ratio of the groups of formula I and/or formula II to the groups of formula III in said double bond-containing diacetylene amide oligomer and polymer is preferably in the range of 0.2<=(III)/(I+II).

Description

[Detailed description of the invention] 3. The invention is based on the invention by Kaisui Kaisho, Ai Itoda, 1 story [Technical field of application of the invention] The present invention provides the The present invention relates to a molded article using a double bond-containing diacetylenic amide oligomer and polymer that has increased crosslinking density and, as a result, has a high modulus of elasticity and good heat resistance.

[Prior art]

In recent years, the synthesis of single-crystal polymers using topochemical reactions through solid-state polymerization has attracted attention, and attempts have been made to use this technique to develop various functional polymers with high elastic modulus. (For example, "Organic Nonlinear Optical Materials", CMC (I985), Macromolecule Chemistry Vol. 134, p. 219 (I970), Journal
of Polymer Science Vol. 89, p. 133 (
I971), Journal Op Polymer Science Polymer Physics Edition Vol. 12 No. 15
Page 11 (I974). ) The present inventors have already synthesized a novel amide group-containing diacetylene compound, and have used this to develop various polymer molded articles having a high elastic modulus.

[Problem to be solved by the invention] Highly elastic molded products can be obtained by crosslinking the diacetylene group-containing amide oligomers and polymers that have been developed so far by utilizing the high reactivity of the diacetylene groups. However, because the crosslinking density was not sufficiently increased, it was difficult for the molded product to have an elastic modulus exceeding 9 GPa.

[Means to solve the problem]

Therefore, the present inventors have conducted intensive research to further increase the modulus of elasticity and improve the heat resistance of molded articles using diacetylene group-containing amide oligomers and polymers. In particular, research focuses on the molecular structure of components that connect diacetylene groups, the reactivity of diacetylene groups, and the reactivity of diacetylene groups when other reactive bonds other than diacetylene groups are introduced into the molecule. In the process, by introducing double bonds in addition to diacetylene groups, we succeeded in further increasing the crosslinking density in the molded product, and as a result of further research,
We have arrived at the present invention.

That is, the present invention provides one or more constituent units of a diacetylene group-containing hydrocarbon group represented by general formula (I) or diacetylene group-containing hydrocarbon group represented by general formula (I) Provided is a molded article using a double bond-containing diacetylenic amide oligomer and polymer in which one or more constituent units of carbon double bond-containing diamide groups are connected via Xl and x2. It is.

R-CEC-C≡C-R'-...(I)-R"-Cmic-C≡C-R3-...(II)-X'-R'-X"
-...-(I[[) (wherein R is a hydrogen atom or a monovalent organic group R1, R2, R3 are a divalent organic group, R4 is a divalent organic group containing a carbon-carbon double bond) (×1, Xi represents an amide group.) In the present invention, R in general formula (I) is a hydrogen atom or a monovalent organic group, and examples of the structure of this organic group include CI, -
, C2H5-1C++1? -, (CH3) zCH-,
(Cl13) 3G-1(CH3)zccHz-, ),
＠寥CH, ◎, ◎cHt-1 may be substituted with an ether bond, ester bond, amide bond, amino bond, imino bond, urethane bond, urea bond, thioester bond, etc.

For example, CI+30CH2-1◎0CH2-, CHz≡
C) I-CHzOCflz-1CH30・, ◎0◎, C
Hz≡CHCHtO◎, CH2≡CHCOO◎, CH3
C0NHC)Iz-, C)lz≡CHCON)lCII
z-1CH3CONH<Hpu, CH3CONHCH2-
etc. Furthermore, some of the monovalent organic groups R and R substituted with other bonds may be substituted with a nitro group, a hydroxyl group, a cyano group, a carboxyl group, an amino group, a halogen atom, or the like.

In the present invention, R1, R2, and R3 are the same or different divalent organic groups, such as -CH2-1C
Examples include complex groups of H, - and alicyclic groups, and these R
1. No matter how many hydrogen atoms in R2 and R3 are substituted with a halogen atom, nitro group, hydroxyl group, cyano group, carboxyl group, amino group, amide group, ester group, carbonyl group, ether bond, etc. good.

In addition, the organic group may include an ether bond, a sulfonyl bond,
It may be an organic group connected by an amide bond, an ester bond, a carbonyl bond, etc. Specific examples include -
CIIzOCHz-,'(YΣ0(feathers, these R1,
Among R2 and R3, -CH2- and -CH-1 direct CH3 CH are preferable because of ease of synthesis and good heat resistance.

stomach.

In the present invention, R4 is 2 containing a carbon-carbon double bond.
is a valent organic group, examples of which are -CIl.CH-
1+CH≡CH+i- (where m is an integer greater than or equal to 2),
-CH2CH≡CH-1-C! IzCIbCIICll
z-, combined CH≡CH-1H2- @c) I=cl (cL-, -C) lzC1hCH≡CI
I-, -CH2CH2CH=cocuz-1■Cl1z
CII≡CH-, CCH≡CH-CCH≡CH, -cl
Some of += are halogen atoms, nitro groups, hydroxyl groups,
It may be substituted with a cyano group, carboxyl group, amino group, amide group, ester group, carbonyl group, or ether bond. Further, the organic group may be connected with an ether bond, a sulfonyl group, a carbonyl group, a carboxyl group, an amide group, etc., and specific examples thereof include -CH, CH
CCH≡CH-1 In the present invention, Xl and X2 are amide groups, and the amide group may be a primary amide group or a secondary amide group, and may be a n) diacetylene group-containing hydrocarbon group and formula (III)
This is a group for connecting with R4 in . That is,
In the present invention, the double bond-containing diacetylene-based amide oligomer and polymer (hereinafter referred to as the diacetylene compound) used as the raw material for the molded article are carbonized diacetylene group-containing compounds of formula (I) and/or formula (II). Hydrogen % Rl and/
Alternatively, it is an oligomer or polymer in which R2, R3 and a divalent organic group R4 containing a carbon-carbon double bond of formula (III) are connected via an amide group (X' or X2).

In the present invention, the diacetylene compound that is the raw material for the molded article is not limited to a homo-oligomer or a homopolymer, and may be copolymerized with other monomers or polymers. Examples of copolymerization include block copolymerization, random copolymerization, graft copolymerization, and alternating copolymerization. Further, it may partially contain other linking groups such as ester groups, imide groups, and ether bonds.

In the present invention, diacetylene group-containing hydrocarbon group formula (■
), the content of formula (II) and carbon-carbon double bond-containing diamide group formula (III) in oligomers and polymers is not particularly limited, but the content of formula (II) and carbon-carbon double bond-containing diamide group in oligomers and polymers is not particularly limited. In order to increase the heat resistance of the product, the total number of moles of the carbon-carbon double bond-containing diamide group of formula (III) is preferably a diacetylene group-containing hydrocarbon of formula (I) and/or formula (II). , More preferably, to illustrate the diacetylene compound which is the material of the present invention, Hl;E(:L;MiCCHz N CCll≡Cll
CH≡CHCNC≡CCECH○
0 +1cmiCC3CCH2CN Ctl≡CHN CC
1(z(,-CG≡CCH:+-CECCHI IC3CC3CCHzN CCII≡CHCNC1h
C≡CC3CHII C1h CH3 HC3CCHz COOCII□CmiCHIll
Il+ +C≡CCH□N CCH≡CII CN CHzC
MiC-)-÷C≡CCHzN CCH≡CHCNC)I
Examples include zC≡C→lower Ill l11 co oc II Il+ CC CC 111It.

The method for producing the diacetylene compound of the present invention includes, for example, a method of polycondensing a raw material (representing an elementary atom or a hydrocarbon group) with carvone (hereinafter referred to as method 1), or a method of polycondensing a metal catalyst such as A method of oxidative coupling polymerization using
(referred to as method 2) is given as an example.

In the case of method 1, for example, amine) (NR"CmiCC= combination, for example, the amine is dissolved in an alkaline 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 HNR"CECCmiCR3NH and carboxylic acid ester, or force X.

The diacetylene compound can also be synthesized by polycondensing rubonic acid HOCR4COH 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 ester or carboxylic acid. This homogeneous polycondensation can also be applied to carboxylic acid halides.

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

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.

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 1 minute to 10 hours.

In the oxidative coupling polymerization of method 2 above, the number of moles of the metal catalyst used is 0. The flow rate of oxygen is preferably from 1 equivalent to 1 equivalent and 10 to 1000 m5/nin. Pyridine is preferable as the solvent used in this reaction, but other solvents can also be used together, depending on the reaction temperature,
There is no particular restriction on the reaction time, and preferably the reaction temperature is between -20°C and 100°C, and the reaction time is 20°C.
The range is from minutes to 12 hours.

In the present invention, the diacetylene compound and the raw materials for its synthesis can be confirmed and identified by infrared spectroscopy (hereinafter referred to as IR), laser Raman method, X-ray method, thermal analysis method, and magnetic resonance method.

The molded article of the present invention is formed by using the diacetylene compound,
It is a molded product formed into a certain shape, and this molded product is basically a molded product in which some or all of the diacetylene bonds and/or double bonds are reacted and hardened.

The shape of the molded body is not particularly limited, and may be, for example, fibrous,
It can be in the form of a film, sheet, membrane, plate, tube, rod, etc., depending on the application, if necessary.
It may be in granular or powder form.

The molded article of the present invention can be produced by compression molding, injection molding, rolling molding, rotational molding or 't8? (Various molding methods such as molding from I and dispersions are used, and there are no particular restrictions, but methods that cause curing during molding or before or after molding are used.Here, curing refers to the cured product. This refers to a state in which the diacetylene compound is softened or not dissolved in the solvent of the diacetylene compound, and is considered to be a state in which a crosslinking reaction is occurring.

Means for causing curing include application of heat, light irradiation, pressure,
Radiation, electron beam irradiation, etc. are used alone or in combination, and the simplest and most effective method is the application of heat and pressurization.

For example, a hardened powder with excellent heat resistance can be obtained by heating the diacetylene compound powder under gas pressure as needed without melting it.

Alternatively, the powder of the diacetylene compound is compressed, and
A hardened compression molded product can be obtained by heating if necessary.

Alternatively, a cured film-like molded product can be obtained by placing or spraying the powder or solution of the diacetylene compound onto a heated object.

In addition, various molding methods such as rotational molding, injection molding, extrusion molding, and rolling molding using the powder of the diacetylene compound are conveniently and effectively used in combination with a heating means, and are preferred.

Preferably, a combination of five compression techniques is used.

In addition, when the diacetylene compound tends to form crystals, a method of growing the crystals and curing the crystals by heating or applying pressure at a temperature below the melting point may also be used.

When obtaining the molded article of the present invention, appropriate conditions for the above-mentioned application of heat and pressurization may be found depending on the characteristics of the diacetylene compound. For example, one method is to perform differential thermal analysis before molding to find out the temperature range in which the curing reaction occurs. Generally, the heating temperature is from room temperature to 400°C, preferably from room temperature to 350°C, and most preferably from 30°C to 30°C as an industrial process for shortening curing and molding time.
It is in the range of 0°C. However, even when the heating temperature is around 250°C or lower, curing is sufficiently progressed, and the molded article of the present invention can be easily produced.

Application of pressure is not necessarily necessary, and depending on the molding method, a reduced pressure system may be used. However, application of pressure is preferable when molding powder into a specific shape, and is also utilized from the perspective of accelerating curing. In general, the degree of pressurization is 5 kg/cl and there is no upper limit, and it can be used up to the limit of industrial static pressure technology.
It is also possible to use impact pressure. Preferred pressure is 1-1
000 MPa, especially 5 to 700 MPa.

In the molded article of the present invention, the diacetylene compound may be used alone, or in addition to the diacetylene compound, thermosetting resins, thermoplastic resins, inorganic substances, metals, carbon materials, stabilizers, flow control agents, release agents, etc. It is also possible to mix mold materials, coloring materials, ultraviolet absorbers, curing accelerators and inhibitors, etc., and the shape of these materials can be changed to not only powder, but also sheets, plates, fabrics, cotton, and fibers, if necessary. It is also possible to use materials formed into shapes such as shapes, grains, flakes, plates, rods, and tubes.

A molded article using the diacetylene compound obtained by the present invention has excellent mechanical properties, for example, an elastic modulus of 4 GPa.
Generally, the elastic modulus is 5GPa or more, depending on the selection of the compound and molding conditions, the elastic modulus is 9GPa or more, and even 1OG
It is also possible to exhibit an elastic modulus of Pa or more.

For the above elastic modulus, depending on the shape of the molded product, bending elastic modulus, tensile elastic modulus, and other methods of measuring elastic modulus can be applied. The standard method for measuring flexural modulus is ASTM-D7.
90-66 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, the following method was used to measure the flexural modulus of the small molded product.

That is, the above method for measuring the bending elastic modulus is as follows: the length of the test piece is 15n+ or more, the width is 4mm, the height is 2+n, the path between the fulcrums is M10y, the fulcrum tip radius is 2R1, the pressure wedge tip radius is 5R1, and the test speed is 51φl. Measurements were made with the settings set to In this case, although the flexural modulus was measured to be slightly smaller than the ASTH method, almost similar values were obtained.

〔Effect of the invention〕

The molded article of the present invention has two components: a double bond and a diacetylene group.
Because it is manufactured using amide oligomers and polymers that have a high density of highly reactive crosslinking groups, the distance between the crosslinking points between molecules in the molded product is extremely short, resulting in a high elastic modulus, and exhibits good heat resistance.

Therefore, the molded article of the present invention can be used in a wide range of fields such as electronic materials, aerospace, precision machinery, and structural materials.
Available.

〔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.

[Example 1] By polymerizing while introducing oxygen gas in the presence of CuCl in a mixed solvent of HC≡CCHz N-lydone obtained by reacting fumaryl chloride and propargylamine in a water-chloroform system, I got it. The polymer (2) thus synthesized was packed into a cylinder of a molding machine shown in FIG. 1, and the pressure inside was reduced using a vacuum pump. Subsequently, the molding machine was placed on a hydraulic press, and molding was performed at a pressure of 3QMPa and a pressure time of 5 minutes at 30°C.
Further, when the molded product was treated under the conditions shown in Table 1 using the hydrostatic pressure apparatus shown in FIG. 2, a molded article having the flexural modulus shown in Table 1 was obtained.

Table 1 Even after heat treatment for hours, no decrease in elastic modulus or weight loss was observed. Further, this molded product was substantially insoluble in m-cresol, formic acid, and N-methylpyrrolidone, which are the solvents for polymer (1).

Example 2 Example 1 was repeated using itaconyl chloride instead of fumaryl chloride.

In this case, the obtained polymer is as follows, and Table 2 shows the elastic modulus of a molded article obtained by molding this polymer (1) in the same manner as in Example 1.

The molding conditions in Table 2 are those when using a hydrostatic pressure device.

m-cresol shown in Table 2 was substantially insoluble in formic acid.

In this case, the obtained polymer is as follows, and Table 3 shows the elastic modulus of a molded article obtained by molding this polymer (1) in the same manner as in Example 1.

The molding conditions in Table 3 are those when using a hydrostatic pressure device.

It was substantially insoluble in m-cresol and formic acid, which are the solvents shown in Table 3.

Example 4 Example 1 was repeated using 11□NQC≡CH in place of propargylamine.

In this case, the obtained polymer is OO, and Table 4 shows the elastic modulus of a molded article obtained by molding this polymer (2) in the same manner as in Example 1.

The molding conditions in Table 4 are those when using a hydrostatic pressure device.

Table 4 The thus obtained molded body showed no change in elastic modulus and weight loss even after being treated at 300°C for 5 hours. A film was formed using a wet method using the dope. This film was heated to 150°C.
By heat-treating for 5 hours, a brown film could be obtained. This brown film showed no weight loss after heat treatment at 210° C. for 18 hours. Moreover, the heat-treated film was insoluble in m-cresol.

[Example 6] Polymer (1) and polymer (2) were blended in a ratio of 1=1 and high-pressure molded at 700 MPa and 180°C for 4 hours in a hydrostatic pressure device. The flexural modulus of the molded product was 14.6 GPa. Ta.

[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.

Claims (1)

[Claims] 1) One or more constituent units of a diacetylene group-containing hydrocarbon group represented by the general formula (I) or (II) and a carbon-carbon group represented by the general formula (III). One or more constituent units of the carbon double bond-containing diamide group are X^1,
Molded product R-C≡C-C≡C-R^1-...(I)-R^2- using a double bond-containing diacetylenic amide oligomer and polymer connected via ^2 C≡C-C≡C-R^3-...(II) -X^1-R^4-X^2-...(III) (wherein, R is a hydrogen atom or a monovalent organic Group, R^1, R^
2, R^3 is a divalent organic group, R^4 is a divalent organic group containing a carbon-carbon double bond, and X^1 and X^2 represent an amide group. ) 2) The ratio of formula (I) and/or (II) and (III) contained in the double bond-containing diacetylenic amide oligomer and polymer is 0.2≦(III)/, [(I )+(II)]≦5 A molded article using the double bond-containing diacetylenic amide oligomer and polymer according to claim 1.