JPH0352905A - Polymerization of diacetylene compound - Google Patents

Abstract

PURPOSE:To obtain a polymer good in formability and operability to be used for e.g. optical elements by polymerization of a liquid diacetylene compound of high shape-imparting capability through heating and/or high energy irradiation while solidifying said compound under a specific elevated pressure. CONSTITUTION:A low-melting liquid diacetylene compound of high shape- imparting capability (e.g. 1,6-dichloro-2,4-hexadiyne) is sealed with e.g. a polyester film and put to heating treatment at 40 deg.C for 60hr and/or high energy irradiation while solidifying said compound under a pressure of >=2 atm. The pressure is then returned to normal level and the reaction product is washed with acetone, thus obtaining the objective polymer with reddish-brown metallic gloss. The above-mentioned pressure is >=2atm.; however, pref. being 5-15000atm. (more pref. 10-5000atm.).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for polymerizing diacetylene compounds, and more specifically to a method for efficiently polymerizing diacetylene compounds with a low melting point using high pressure. It is related to. [Prior Art] In recent years, the synthesis, formation, and mechanization of various diacetylene compounds as raw materials for nonlinear optical materials, semiconductor crystals, and high-modulus materials have been extensively studied. The present inventors also crosslinked a compound having a diacetylene group and a carbon-carbon double bond to produce a material with a high elastic modulus exceeding 20 GPa.

The diacetylene compounds that have been studied so far are one JQ
It is converted into the corresponding polydiacetylene compound by solid phase polymerization (toboke ξ cal polymerization). Since the obtained boridiacetylene is generally insoluble and infusible, it is generally given the necessary shape before polymerization in order to use it as an element or shaped body. However, diacetylene compounds that are generally studied have a molecular structure that has a high melting point due to dipole-dipole interaction, hydrogen bonding, etc. in order to perform solid phase polymerization. Therefore, since such diacetylene compounds undergo rapid polymerization and decomposition as soon as they reach their melting point, it is extremely difficult to give them a shape in the molten state.

On the other hand, diacetylene compounds with a low melting point, that is, liquid at around room temperature or below, can be easily formed into a desired shape in a heptamer state, but the polymerizability of these diacetylene compounds is generally low. Hasegawa et al. disclose a method of photopolymerizing a diacetylene compound with a melting point of 20°C or less after solidifying it at a low temperature (synth. Met.. 18.41
3 (1987)) uses ultraviolet light as a light source and is therefore not suitable for polymerizing large amounts of thick diacetylene compounds. Furthermore, the types of diacetylene compounds that can be polymerized by this method are extremely limited. [Problems to be Solved by the Invention] An object of the present invention is to provide an effective method for polymerizing a liquid diacetylene compound, which is excellent in formability and operability, and can improve the polymerization rate and polymerization rate. It's about doing. [Means for Solving the Problem] In the process of investigating various efficient polymerization methods for low-melting diacetylene compounds with high shape-imparting ability, the present inventors placed diacetylene compounds under high pressure and After giving the material a suitable shape, it was found that if it was solidified and then heat or light was applied while the material was under high pressure, the polymerization of diacetylene groups could proceed very easily.

Furthermore, as a result of extensive research into the relationship between the pressure in high-pressure solidification and the molecular structure of diacetylene compounds, and the polymerization conditions, the present invention was achieved. That is, the present invention is a method for polymerizing a diacetylene compound, which is characterized by polymerizing a liquid diacetylene compound by heating and/or high-energy irradiation while solidifying the compound under a pressure of 2 atmospheres or more.

In the present invention, a liquid diacetylene compound R-CmiC
The chemical structure of CMC-R' (R and R' represent different or similar organic groups) is not particularly limited, but from the viewpoint of ease of handling, it has a temperature of -10°C to 50"C at normal pressure. Diacetylene compounds with melting points in the vicinity are preferred.

The diacetylene compound (R-C=CCfC
-R' of R. An example of R' is -CH. (/!
, -CH. Br+-CHzP, CHzCHzC
l, C}l! OCH3. CHzCtbO
Ctb, ■ CHzOCHzCH. CHzCH+. CTo
CH1CHJCIh, CHJ(CHs)1CHzCCH
3. CHzOOCCH3l book) 0 CHzCHzOOCCH. Examples include CHzCH.

0 A method for solidifying a liquid diacetylene compound under high pressure includes a method in which the diacetylene compound is sealed in advance in a bag made of polyester, nylon, Teflon, etc., and then solidified under solid pressure, gas pressure, or hydrostatic pressure. As a method for applying high pressure, a gas pressure method and a hydrostatic pressure method are preferred, and a hydrostatic pressure method is particularly preferred because of ease of handling. It can be confirmed whether the diacetylene compound has solidified or not by installing a window on the pressure generator and visually observing it directly from there. However, in general, the rate of increase in the melting point of organic substances is about 20 to 30 degrees Celsius when pressurized at 1000 atm.
It can be roughly determined from this scale. To accurately measure the melting point under high pressure, high-pressure differential thermal analysis (high-pressure DTA) or high-pressure differential scanning calorimetry can be applied. The pressure range is 2 atm or more, preferably from 15,000 atm due to the rate of increase in the melting point, and more preferably from 10 atm to SO to suppress the decomposition of the compound.
oo atmospheric pressure. As described above, after confirming that the liquid diacetylene compound has solidified under a pressure of 2 atmospheres or more, the diacetylene compound can be polymerized by heating and/or high energy irradiation.

The heating range is preferably 35°C to 300°C, and in terms of suppressing decomposition, the heating range is 35°C to 20°C.
0°C is more preferable. If the diacetylene compound decomposes under high pressure, heating may be performed depending on the polymerizability and stability of the diacetylene compound, such as applying pressure at a low temperature of 0° C. or lower and then gradually increasing the reaction temperature. It is preferable to choose the heating rate.

High-energy irradiation sources include ultraviolet rays, electron beams,
, γ rays, α rays, etc., and the irradiation time and irradiation amount can be arbitrarily determined depending on the reactivity of the liquid diacetylene compound.

Heating and light irradiation can be combined as necessary. Polymerization of the liquid diacetylene compound can be confirmed by the fact that insoluble matter remains after the pressure is released.

In particular, when the diacetylene polymer has an en-yne structure or a butatriene structure, a unique coloration such as red, blue, or purple is observed. The structure of the produced polymer was determined by infrared absorption spectrum (IR), Ramanance vector, and solid-state NMR.
It can be easily determined by general-purpose analytical means such as spectroscopy.

〔Effect of the invention〕

The present invention shows an effective method for polymerizing liquid diacetylene compounds with excellent formability and operability. According to the present invention, liquid diacetylene compounds, which have rarely been used in the past, can be easily polymerized, thereby significantly expanding the range of diacetylene compounds that can be used industrially. In addition, since the polymerization reaction proceeds under high pressure, the present invention is novel from a higher-order structural perspective, such as obtaining a boridiacetylene compound having a crystal structure in a high-pressure phase that cannot be obtained by normal-pressure solid-phase polymerization. A boridiacetylene compound can be provided.

In reaction systems where the volume decreases in the transition state, such as the polymerization reaction of diacetylene compounds, the reaction rate and reaction rate can be increased by increasing the pressure. Therefore, it can be said that the polymerization method of the present invention is an extremely excellent method for improving the polymerization rate and polymerization rate. As described above, it can be seen that the present invention has many features and characteristics not found in conventional polymerization reaction methods for diacetylene compounds, considering the chemical structure, higher order structure, and reaction aspects. Therefore, the boridiacetylene compound obtained by the present invention is very useful as an optical element, a conductive material, and a high-strength, high-modulus material.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. [Example 1] Polymerization of C f cnxcmi CCiFCCHzC f 1,
6-dichloro-2,4-hexadiyne 5d was sealed with a polyester film and heated under a hydrostatic pressure of 5000 atm for 4 hours.
Heat treatment was performed at 0°C for 60 hours. (Solidification of the sample was confirmed under these conditions using high-pressure DTA.) After heat treatment,
The pressure was returned to normal pressure and the resulting reaction product was washed with acetone. A polymer with a reddish-brown metallic luster was obtained with a yield of 24%. The obtained polymer was found to be a polymer having an en-yne structure by analysis of infrared absorption spectra, solidified NMR spectra, Ramanth vectors, etc. Furthermore, it was revealed from powder X-ray diffraction that the obtained polymer had extremely high crystallinity.

I R (CI-'): 1425. 1326.
1261, Ramance vector (cm-'): 22
10, 1590 [Example 2] Polymerization of BrCHzC=CC=CCzBr 1,6-dibromo-2,4-hexadiyne 5II1. After sealing with polyester film, 3000 atm, 100 hours,
Heat treated at 50°C. (Solidification of the sample was confirmed under these conditions by high-pressure DTA.) After the treatment, the precipitated polymer was isolated by suction filtration and washed repeatedly with acetone. A reddish-brown polymer was obtained with a yield of 38%. Analysis of Raman spectra and infrared absorption spectra revealed that the obtained polymer had an en-yne structure. [Example 3] CtHsCOOCHzC! 'CCi'CCHz00CC
Polymerization of tHs 2,4-hexadiyn-1,6-diol dibropyrolate 3Id at 6500 atm for 60 hours, 8
Heat treated at 0℃. (Solidification of the sample was confirmed under these conditions by high-pressure DTA.) After the heat treatment, an insoluble and infusible polymer was obtained almost quantitatively. Analysis of infrared absorption spectra, elemental analysis, Ramans vector, etc. revealed that it was a polymer with an almost en-in structure. [Example 4] Polymerization of CToOCHzCffCCWCCRzOCH3 1
．． Example 3 was repeated except using 6-dimethoxy2,4-hexadiyne. After the heat treatment, a black insoluble and infusible polymer was obtained almost quantitatively. infrared absorption spectrum,
Elemental analysis, Ramans vector analysis, etc. revealed that it was a polymer with an almost en-in structure. [Example 5]? CL) tNcH■C=CC5CCHgN(CH!)
*Polymerization of N. N. N'. N'-tetramethyl-
Example 3 was repeated except that 1,6-diamine-2,4-hexadiyne was used. After heat treatment, a black insoluble and infusible polymer was obtained almost quantitatively. infrared absorption spectrum,
Analysis such as elemental analysis and Raman spectra revealed that it was a certain polymer based on the almost en-in structure.

[Example 6] 1.6-dichloro-2.4-hexazine sealed with a polyester film was placed in a high-pressure hydrostatic pressure device equipped with an optical window made of polymerized sapphire of C f CHtC'CC=CCIhCl, and the temperature was increased to 5000 atm. , solidified at 20°C.
The thus solidified sample was irradiated with ultraviolet light for 1 hour. Red coloring due to the polymer was observed along with ultraviolet irradiation.

The polymer yield at this time was 36%. Similarly, instead of ultraviolet rays, electron beams, X-rays, and radiation (γ-rays) were irradiated for one hour. The polymer yields at this time were 58% and 52%, respectively.
%, 86%. For comparison, 1,6-dichloro-2,4-hexadiine solidified at -30°C under normal pressure was irradiated with ultraviolet rays for 1 hour, and the polymer yield was 8.2%.
Met. Furthermore, electron beams, X-rays, and radiation (γ-rays) were used instead of ultraviolet rays, but the polymer yield did not exceed 50%. [Example 7] Example 6 (ultraviolet irradiation) was repeated except that the polymerization temperature was changed to 40°C instead of 20°C. The polymer yield at this time was 46%.

Claims (1)

[Claims] 1. A method for polymerizing a diacetylene compound, which comprises polymerizing a liquid diacetylene compound by heating and/or high-energy irradiation while the diacetylene compound is solidified under a pressure of 2 atmospheres or more.