JPS62288612A - Molded article using amino group-containing polydiacetylene - Google Patents

Abstract

PURPOSE:A molded article obtained by molding an amino group-containing polydiacetylene prepared by polymerizing a specific amino group-containing diacetylene compound and having a high elastic modulus and strength. CONSTITUTION:A molded article obtained by molding an amino group-containing polydiacetylene prepared by polymerizing an amino group-containing diacetylene compound expressed by the formula (X, X', and Y and Y' are H or 1-20C hydrocarbon; R and R' are 1-10C aliphatic hydrocarbon or alicyclic hydrocarbon), preferably under a high pressure. USE:Electronic materials, nonlinear optical materials, etc.

Description

Detailed Description of the Invention [Technical Field of Application of the Invention] The present invention relates to a molded article using an amino group-containing polydiacetylene, and more specifically to a molded article using an amino group-containing polydiacetylene that is obtained by polymerizing with a diacetylene group. This relates to molded products using acetylene.

[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 develop various highly crystalline polymers with high elastic moduli using this technique.

(For example, "Organic Nonlinear Optical Materials" CMC (1985), Macromolecule Chemistry Vol. 134, p. 219 (1970), Journal of Polymer Science Vol. 89, p. 133 (1971), Journal
of Polymer Science, Polymer Physics
Edition Vol. 12, p. 1511 3, (1974)
)' [Problem to be solved by the invention] However, the diacetylene compounds with topochemical polymerizability that have been synthesized and researched so far have +
The research has been limited to metal compounds and derivatives thereof having hydroxyl groups such as 10cH2c=C-CmiCCH20H, 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 the nitrogen atoms can be utilized, and if the nitrogen atoms have -N11- 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.

However, hardly any amino group-containing diacetylene compounds exhibiting such topochemical reactivity have been found so far. For example, although an amino group-containing diacetylene compound in which an aromatic ring is bonded next to a tyrene bond is already known, this compound has not been recognized to have topochemical properties.

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 polydiacetylene compound containing an amino group. However, as a result of further research, we have arrived at the present invention.

That is, the present invention is based on the general formula (where, one or more groups or atoms selected from the following, R and R' represent an aliphatic hydrocarbon group or an alicyclic hydrocarbon group having 1 to 10 carbon atoms). The present invention provides a molded article using the amino group-containing polydiacetylene obtained.

In the present invention, X, X', Y, and Y' are each 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 hydrocarbon groups having 1 to 20 carbon atoms include CI+3, CtHs, C, H, Ca 119,
CsH+ r, CJrjSC? 1IIS%CsH+t
, CJIIq , Cl. 11□C1l□=CH-,C
LCH=CH-, IIc E C-1HC= CC1h
-, PhCHz- and other aliphatic hydrocarbon groups, and aromatic hydrocarbon groups, and the above aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups are halogen atoms and nitro groups. , 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, 2-CO- or Z
-3O, - (z represents the hydrocarbon group); examples include CHaC-1CzllsC
-1C*lI+C-1Cal amount qC-1PhC-1Ph
C) It C-, CH25O*-, CJsSOt-1C
3H1SOt-1CJwSOt, Ph5Ot 5Ph
CHxSOz- and the like are preferred.

Examples of the halogen atom include FSCl, Br, and I, preferably CI and 3r.

In the present invention, as X, Y, X', Y',
A preferred combination of (X, Y, X', Y') is
(H, H, H, H) (H, C)12. H, CH3)
(H9CJs, HlCtHs) (H, C5kIr,
H, C1Hy) (H, C4119, H, C4H9)
(H, Cs1lll, H, C3H11) (H, CJI
I, H, CJII) (H, C?HIS, H, CJ+5)
(H, CtH+t, H, CIHI?) (H, C9H1
9, H, C9L9) (H, C+Jz+, H, Cto
Hzi) (H, CtJ*s, H.

ClJzs) (H,C+5Hsv, H,CtsHs7
) (H, CzJIa□H, CtOI+41) (H,
CL"CH-+H+ CH2=CH-) (H.

Cl13CH=CH-, H, C113CH, C11-)
(H, uc=c-, H, IIc=C-) (H, H
C=CCHz-1H, IIC=CCHg-) (1(
.

(H,C)IzS(h-,H,CthSOz-)
(H, CI 3NS (h-, H.

■ C1hSOz-) (H, Ph5O□, H, Ph5
Oz-) (H, Cj!

H, Cl2) (H, Br, H, Br) (H1 ■,
Fertilization I) (CH:l, CH3, CIl+, C1h)
(C1li, CtHs, C1h, Czlls) (
C1lz, Ph, CJs, H) (H, CIl
=Cl1. CH3,C,)l? )(C2H5, CIl
□=C1l, CH3, CJt) (H, HC= CC
II□-1CH3,CzHs) (CH3,HC=CC
Hz-, Czlls, CJt) (H.

C2H5, C3H? ) (C1ls, C1hSOz
, ph, CH3-) (CHz, Br, Ph
, CHyC-) (CJs, L C7!, ■-
1) (CJt, C(1, Br, H) (C1, C1,
CJt, (J) (Br, Br, Br, Br
) (Br, Br, Br, I) (
CIl CH:l.

CHz C-, CH35O□-) (C113, CH
35O□-, C2H5, Ph) (C8, So□, C)
1350□, CIl:1sO2, C1hSOz), etc. Particularly preferred is the case where both x and x' are hydrogen atoms, since this is excellent in terms of topochemical properties due to improved cohesive force. It is.

In the present invention, R, R' are C113CH
3CH3 -COz-, -CH-, -C-, -C-, -CzH4-
, -Cl6-1CH3C2H5 CH3Cl+! -CHzCH-1-CJs-1-CHz-C-CHz-
, -C5H1゜-9■ CH.

1□. IH3, preferably -CI+2- for ease of synthesis
.

CH, lCHs -C2H,, -, -CH-, -C-.

C)13 In the present invention, n is not particularly limited other than a positive integer of 2 or more, but is preferably a positive integer of 50 or more in order to have sufficient moldability and strength.

In the present invention, the weight percent of the diacetylene group-containing polyamide in the molded article using the amino group-containing polydiacetylene is not particularly limited, and it may be blended or copolymerized with other monomers or polymers.

The chemical structure of the amino group-containing polydiacetylene, which is the raw material for the molded product using the amino group-containing polydiacetylene of the present invention, has been confirmed by infrared spectroscopy, laser Raman, X-ray method, nuclear magnetic resonance method, etc. The basic repeating unit is that the diacetylene group in the raw material monomer is trans-1
, 4-addition of formula (■), formula (2), or an equilibrium mixture of formula (1) and formula (2) is suggested.

However, some of the repeating units of the amino group-containing polydiacetylene may partially contain repeating units other than formula (1), formula (2), or an equilibrium mixture of formula (2) and formula (2).
For example, formulas such as Formula ■, Formula ■, which is a cis-1,4-addition of the raw material monomer, Formula ■, Formula ■, or an equilibrium mixture of Formula ■ and Formula ■; It's okay.

The above-mentioned amino group-containing polydiacetylene may also be used.

A method for producing an amino group-containing polydiacetylene, which is a raw material for the amino group-containing polydiacetylene of the present invention, and a photopolymerization method using a low pressure, medium pressure, Y' or high pressure mercury lamp. It can be synthesized by polymerization using a UV irradiation method, an electron beam irradiation method, a γ-ray irradiation method, or a plasma polymerization method.

On the other hand, as a thermal polymerization method, it can be synthesized, for example, by treating the raw material at around the melting point or decomposition point of the material for a certain period of time.

On the other hand, as a pressurization method, synthesis can be performed, for example, by pressurizing raw material monomers for a certain period of time.

When producing the above amino group-containing polydiacetylene,
The above-mentioned photopolymerization method, thermal polymerization method, and pressurization method may be used alone, but two or more may be used in combination.For example, a method of producing by pressurization while heating can also be applied, and is rather preferable. . In the above photopolymerization method, thermal polymerization method, and pressure method, a polymerization accelerator such as a peroxide, an azo compound, a disulfide, a halogen compound, a carbonyl compound, etc. may be used.

The system for carrying out the polymerization method may be in the form of a lump, solution, suspension, emulsion, or solid phase, but is particularly preferably a solid phase. However, a single crystal is particularly preferable.

In the above method for producing an amino group-containing diacetylene compound, there are no restrictions on the light source used in the photopolymerization method, the output of the light source, the distance between the light source and the raw material monomer, and there is no restriction on the reaction time, preferably 1 second. It's been 10 hours since.

On the other hand, in the thermal polymerization method, the reaction temperature is not particularly limited, but is preferably from a temperature 50°C lower than the melting point or decomposition point of the raw material to the melting point or decomposition point, and there are no restrictions on the reaction time. The time is preferably from 10 minutes to 10 hours.

On the other hand, in the pressurization method, the pressure is not particularly limited, but is preferably from 11,000 at to 10,000 at I11, and the reaction time is also not limited, preferably from 1 hour to 10 hours.

When producing the above-mentioned 7-mino group-containing polydiacetylene,
It is extremely important that the raw material monomer has a high degree of purity.
Those with a purity higher than that are preferable. To obtain such highly pure raw material monomers, general purification methods such as distillation, recrystallization, and sublimation can be used.

To determine the purity and structure of the raw material monomers used in the present invention and the amino group-containing polydiacetylene obtained by polymerizing the raw material monomers, IR (infrared absorption spectroscopy), N
MR method (nuclear magnetic resonance method), liquid chromatography method, and thin layer chromatography method are suitable.

The molded article using the amino group-containing polydiacetylene of the present invention can have various forms and is not particularly limited, such as powder,
Examples include single crystal, fiber (multifilament, chopped strand, monofilament), fibrid, film, nonwoven fabric, sheet, plate, rod, flake, plate, etc. Particularly preferred are powder, single crystal, fiber,
It's a film.

The method for producing a molded article using the amino group-containing polydiacetylene of the present invention is not particularly limited, and examples thereof include compression molding, injection molding, wet spinning, melt spinning, and the like.

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.

Pressure is not particularly limited, but preferably 150 kg
/cu1 or more, particularly preferably 1000kg/cu
cn1 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.

As the elastic modulus in the present invention, bending elastic modulus or tensile elastic modulus can be applied depending on the shape of the molded product. The standard method for measuring flexural modulus is ASTM-D790-6.
6 can be used. However, the molded product of the present invention is not necessarily A
There are cases where it is not always possible to manufacture a molded article large enough (long enough) to be measured using the STM 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 modulus of elasticity used in the present invention is to use a test piece with a length of 15 or more, a width of 4, and a height of 2. The distance between the fulcrums is 10, and the radius of the tip of the fulcrum is 2R1. The radius of the pressure wedge tip is 5R1 Test speed was set at 5 H/min for measurement. In this case, although the flexural modulus was measured to be slightly smaller than the ASTM method, almost similar values were obtained.

〔Effect of the invention〕

The molded article using the amino group-containing polydiacetylene of the present invention has high strength and high elastic modulus due to the cohesive force of the amino group, and is also crosslinked by topochemical reaction by the diacetylene group. Therefore, it exhibits even higher strength and higher elastic modulus.

Therefore, molded products using the amino group-containing polydiacetylene 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, etc.
Furthermore, 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 solid phase reactivity.

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. is very easy to perform (secondary high functionality can also be expressed).

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained using 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.

Moreover, the reagents used in the examples may be purified as necessary, and this is preferable.

[Example 1] was dissolved in 200ml of pyridine and reacted for 50 minutes while blowing oxygen gas. After the reaction, it is isolated by precipitation,
The product recrystallized with methanol was molded into a mold of 1 cm
1 cm x 1 cm, and using a press, press 3
00 atm for 5 minutes.The molded product thus formed is further heated at 6000 atm using a high pressure molding machine.
, 5 hours at 100°C.

After preforming, the flexural modulus was 7.6 GPa, and after high pressure molding, it was 13.3 GPa, both of which show high modulus of elasticity.

[Example 2] 1 mole in 50 ml of methanol-hydrochloric acid mixture,
HJCIh-C= obtained by reacting at 60°C for 6 hours
(Example 1 was repeated except that Cff1CCHtNHz was used. In this case the flexural modulus was 9.3 GPa after preforming and 13.8 GPa after high pressure forming.
It becomes GPa.

Example 3 Example 1 was repeated except using CH. In this case, the flexural modulus is 9.80 Pa after preforming and 16.7 GPa after high pressure molding.

[Example 4] CIIzCNCllgCECH ((Rini[;lIg
Example 1 was repeated except that W-CH was used for =CH-N CH,. In this case, the flexural modulus is 7.2 GPa after preforming and 12.2 GPa after high pressure forming. I
It becomes GPa.

[Example 5] Example 1 was repeated except that before preforming, thermal solid state polymerization was performed at 120° C. for 5 hours under a nitrogen stream. In this case, the flexural modulus after preforming is 9. l GPa, but after high pressure molding it is 13.
8 GPa.

Example 6 Example 1 was repeated, except that before preforming in Example 1, UV irradiation was applied for 6 hours to photopolymerize. In this case, the flexural modulus is 9.3 GPa after preforming, but becomes 13.9 GPa after high pressure molding.

[Example 7] is obtained. This is dissolved in N,N-dimethylformamide, cast on a glass plate, and left at 50°C for 10 hours while irradiated with UV to form a film. This film exhibits an elastic modulus of 12.3 GPa.

[Example 8] The N,N-dimethylformamide solution of Example 7 was wet-spun to produce fibers. When this fiber is heat-treated at 190°C for 10 minutes, it has a strength of 13.4 GPa in the fiber axis direction and a strength of 14
．． It shows 8g/d.

[Example 9] Recrystallize from methanol to produce a single crystal. This is 15
Thermal polymerization is performed at 0°C for 18 hours to produce a polymer single crystal. This shows a compression modulus of 15.8 GPa.

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, X, Y, X', Y' are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, Represents one or more groups or atoms selected from a bonded carbonyl group or sulfonyl group and a halogen atom, R and R' are an aliphatic hydrocarbon group having 1 to 10 carbon atoms, A molded product using amino group-containing polydiacetylene obtained by polymerizing alicyclic hydrocarbon groups.