JP5237762B2 - Cis-cisoid type substituted acetylene polymer and process for producing the same - Google Patents

Description

The present invention relates to a process for producing a cis-cisoid type substituted acetylene polymer from a cis-transoid type substituted acetylene polymer, and a cis-cisoid type substituted acetylene polymer obtained thereby.

As a method for producing a cis-type substituted acetylene polymer, for example, a terminal acetylene polymerization method using a rhodium complex catalyst is known. The cis-type substituted acetylene polymer has two conformations of a transoid structure and a cisoid structure. It exists and each is known to take a helical structure. In this helical structure, it has been reported that the cisoid structure has a shorter helical pitch than the transoid structure and has a dense helical structure (see Non-Patent Document 1).
In any structure, the substituents are oriented as side chains outside the helical main chain. When such side chains have functional groups capable of interacting with each other, the cisoid type, which is a denser helical structure, strengthens the interaction between the side chains, stabilizes the helical structure, and is guided by the side chains. Various functions are more strongly expressed. As described above, a cis-substituted acetylene polymer having such a cisoid structure, that is, a cis-cisoid-substituted acetylene polymer (hereinafter abbreviated as “cc-type substituted acetylene polymer”) is a very useful polymer.

As a method for producing a cc-type substituted acetylene polymer, for example, a method of polymerizing 4-alkoxyphenylacetylene in a hexane solvent is known (see Non-Patent Document 1). However, the chloro (norbornadiene) rhodium dimer generally used as a polymerization catalyst for cis-type substituted acetylene polymers does not necessarily have a high catalytic activity in a low-polar solvent such as hexane. When industrial production is assumed, it is necessary to use such an expensive noble metal compound catalyst at a dilute concentration, so that the reaction rate is extremely low and it is difficult to efficiently produce a cc-type substituted acetylene polymer. On the other hand, in a polymerization reaction in a highly polar solvent such as alcohol or amine, the catalytic activity is higher than that in a low polarity solvent. However, the polymer produced is a cis-transoid substituted acetylene polymer (hereinafter referred to as “ct substituted acetylene”). Abbreviated as “polymer”).

Moreover, it is known that a cis type substituted acetylene polymer will change a color, a structure, etc. with an organic solvent vapor | steam (for example, nonpatent literatures 1-3, patent document 1). However, the treatment with the organic solvent vapor is harmful to the human body, risks of ignition and explosion, and is not necessarily an industrially advantageous method.
Further, it is known that the color and structure of a cis-type substituted acetylene polymer change due to heat (for example, Patent Document 1). However, Patent Document 1 does not describe how to obtain a substituted acetylene polymer having a changed structure by heating the substituted acetylene polymer and then heating it.
From the above, there is no known method for producing an industrially advantageous cc-type substituted acetylene polymer.

Tabata, Mawatari, Polymer, 55 (12), pp 938-941 (2006) Tabata, Sone, Sadahiro, Kaoru, Kobayashi, Inaba, Yokota, Polymer Journal, 54, No. 12, pp 863-874 (1997) MASAYOSHI TABATA et al, J. M. S.-PURE APPL. CHEM., A34 (4), pp641-653 (1997) JP 2007-314750 A

Accordingly, an object of the present invention is to provide an industrially efficient method for producing a cc-type substituted acetylene polymer.

The present inventors diligently studied and found that the above-mentioned object can be achieved by polymerizing substituted acetylene in a polar solvent followed by heat treatment, and reached the present invention.
That is, the present invention provides the following (1) general formula (I)

[Wherein n is an integer of 10 to 100,000. R represents 4- (n-octyloxy) phenyl group or 4- (n-heptyloxy) phenyl group ]
A process for producing a cis-cisoid type substituted acetylene polymer, characterized in that the powdered cis-transoid type substituted acetylene polymer represented by the formula:
(2) The powdery cis-transoid type substituted acetylene polymer has the general formula (II)

[Wherein, R represents the same group as in the general formula (I)]
The method for producing a cis-cisoid substituted acetylene polymer according to the above (1), which is an acetylene polymer obtained by polymerizing the substituted acetylene represented by the formula 8-10 metal compound, and (3) the heat treatment The cis-transoid type substituted acetylene polymer is exposed to hot air under either an inert gas atmosphere or an air atmosphere, or the cis-transoid type substituted acetylene polymer is placed in a sealed container. Additionally or heating the container to a predetermined temperature, to provide a manufacturing how the cis-cisoid type substituted acetylene polymer according to (1) or (2) performed by either.

According to the present invention, a cc-type substituted acetylene polymer can be provided industrially efficiently. The cc-type substituted acetylene polymer obtained in this way has a high density because it has a dense helical structure, and the side chains located in the vicinity are highly aligned with each other, so that the conductive material, electroluminescent material, electromagnetic wave Suitable for highly functional materials such as shielding materials and gas adsorbents.

According to the present invention, a cc-type substituted acetylene polymer can be provided. The present invention will be described in detail below.
In the said general formula (I), n represents a number average degree of polymerization, and is an integer of 10-100,000, Preferably, it is 100-100,000. By setting n to 100 or more, it is preferable because the moldability of the obtained cc-type substituted acetylene and the mechanical strength of the obtained molded article are more excellent, but considering the production cost and molding cost of the cc-type substituted acetylene polymer , 100,000 or less is preferable. The number average molecular weight of the ct-type or cc-type substituted acetylene polymer having n of 10 to 100,000 is about 1000 to 30,000,000. Under the reaction (polymerization) conditions described later, the number average molecular weight of the ct-type (and cc-type) substituted acetylene polymer obtained decreases when the temperature is lowered, the reaction time is shortened, or the concentration of the substituted acetylene is lowered. .
The number average molecular weight of the ct-type or cc-type substituted acetylene polymer having n of 10 to 100,000 is about 1,000 to 30,000,000. Under the reaction (polymerization) conditions described later, the number average molecular weight of the ct-type (and cc-type) substituted acetylene polymer obtained decreases when the temperature is lowered, the reaction time is shortened, or the concentration of the substituted acetylene is lowered. .
In the above general formulas (I) and (II), R is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 4 to 30 carbon atoms, CO ₂ R ¹ (wherein R ¹ represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an aryl group having 4 to 30 carbon atoms which may have a substituent). Ester group shown, CONR ² R ³ (wherein R ² and R ³ each independently have a hydrogen atom, a C 1-30 alkyl group which may have a substituent, or a substituent. An amide group represented by a C 4-30 aryl group, a CO ₂ M (wherein M represents a hydrogen atom or a monovalent metal) or a metal salt thereof. Represents.
Among these, an aryl group having 6 to 10 carbon atoms having a substituent is preferable from the viewpoints of availability of raw materials, ease of monomer synthesis, stability of the cc structure in the polymer, and the like.

[Description of C1-C30 alkyl group]
In the general formulas (I) and (II), examples of the alkyl group having 1 to 30 carbon atoms represented by R, R ¹ , R ² and R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Linear, branched or cyclic such as isobutyl, tert-butyl, hexyl, heptyl, octyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl An alkyl group is mentioned. These alkyl groups may have a substituent. Examples of the substituent include aryl groups such as a phenyl group, a naphthyl group, a pyridyl group, a thienyl group, a furyl group, and a pyrrolyl group; a methoxy group and an ethoxy group. N-propoxy group, isopropoxy group, n-butoxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, cycloheptyloxy group, n-octyloxy group, cyclooctyloxy group, n-decyloxy Group, alkoxy group such as n-dodecyloxy group; alkylthio group such as methylthio group, ethylthio group, propylthio group, butylthio group, phenylthio group, naphthylthio group; tert-butyldimethylsilyloxy group, tert-butyldiphenylsilyloxy group Trisubstituted silyloxy groups such as acetoxy , Propanoyloxy group, butanoyloxy group, pivaloyloxy group, benzoyloxy group and other acyloxy groups; methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group and other alkoxycarbonyl groups; methyl sulfoxide group, ethyl sulfone group Sulfoxide groups such as a xoxide group and a phenyl sulfoxide group; Sulphonic acid ester groups such as a methyl sulfonyloxy group, an ethyl sulfonyloxy group, a phenyl sulfonyloxy group, a methoxy sulfonyl group, an ethoxy sulfonyl group, and a phenyloxy sulfonyl group; a dimethylamino group Primary or secondary amino group such as diphenylamino group, methylphenylamino group, methylamino group, ethylamino group; acetyl group, benzoyl group, benzenesulfonyl group, ter -It may be substituted with an alkyl group or an aryl group, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, or a phenyl group, which is substituted with a butoxycarbonyl group or the like. Amino group; hydroxyl group; cyano group; nitro group; halogen atom such as chlorine atom, bromine atom, iodine atom and fluorine atom;
Preferred substituents are an aryl group, an acyloxy group, an alkoxycarbonyl group, a sulfoxide group, a sulfonate group, a hydroxyl group, and an amino group.

[Description of aryl group having 4 to 30 carbon atoms]
In the general formulas (I) and (II), examples of the aryl group having 4 to 30 carbon atoms, preferably 6 to 10 carbon atoms represented by R, R ¹ , R ² and R ³ include a phenyl group and a naphthyl group. Aromatic heterocyclic hydrocarbons; heterocyclic rings such as pyridyl group, naphthyl group, thienyl group, furyl group, pyrrolyl group; and the like. These aryl groups may have a substituent, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a heptyl group, Linear, branched or cyclic alkyl groups such as octyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; vinyl group, allyl group, crotyl group, prenyl group, 7-octenyl group Alkenyl group such as cyclohexenyl group; alkynyl group such as ethynyl group, propynyl group, propargyl group, phenylethynyl group; methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butoxy group, n-hexyl Group, n-heptyl group, n-octyl group, cyclohexyloxy group, Alkoxy groups such as loheptyloxy group, n-octyloxy group, n-decyloxy group and n-dodecyloxy group; alkylthio groups such as methylthio group, ethylthio group, propylthio group, butylthio group, phenylthio group and naphthylthio group; tert -Trisubstituted silyloxy groups such as butyldimethylsilyloxy group and tert-butyldiphenylsilyloxy group; Acyloxy groups such as acetoxy group, propanoyloxy group, butanoyloxy group, pivaloyloxy group, benzoyloxy group; methoxycarbonyl group, ethoxy Alkoxycarbonyl groups such as carbonyl group and n-butoxycarbonyl group; Sulfoxide groups such as methyl sulfoxide group, ethyl sulfoxide group and phenyl sulfoxide group; Methyl sulfonyloxy group, ethyl Sulfonic acid ester groups such as sulfonyloxy group, phenylsulfonyloxy group, methoxysulfonyl group, ethoxysulfonyl group, phenyloxysulfonyl group; dimethylamino group, diphenylamino group, methylphenylamino group, methylamino group, ethylamino group, etc. A primary or secondary amino group; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert, substituted with acetyl, benzoyl, benzenesulfonyl, tert-butoxycarbonyl, etc. -An amino group which may be substituted with an alkyl group or an aryl group such as a butyl group or a phenyl group; a hydroxyl group; a cyano group; a nitro group; a halogen atom such as a chlorine atom, a bromine atom, an iodine atom or a fluorine atom It is done.
Preferred aryl groups are an optionally substituted phenyl group and an optionally substituted naphthyl group.
Preferred substituents are an alkoxy group, an acyloxy group, an alkoxycarbonyl group, a sulfoxide group, a sulfonate group, a hydroxyl group, and an amino group.

[Explanation of M]
As the monovalent metal that can be taken by M in CO ₂ M which is one of the substituents R in the general formulas (I) and (II), alkali metals such as lithium, sodium and potassium, and copper (I), Examples include transition metals such as silver. Of these, alkali metals are preferable.

〔Production method〕
In the present invention, the cc-type substituted acetylene polymer is synthesized by two steps represented by the following chemical reaction formula. That is, a step of obtaining a ct-type substituted acetylene polymer as a raw material in Step 2 by polymerizing substituted acetylene represented by the general formula (II) in the presence of a Group 8-10 metal compound (hereinafter abbreviated as “Step 1”). ) And ct-type substituted acetylene polymer are heat-treated to obtain the target compound cc-type substituted acetylene polymer (hereinafter abbreviated as “Step 2”).

Details will be described below for each process.
<Step 1 (catalyst)>
Examples of the group 8-10 metal compound used when polymerizing substituted acetylene include rhodium complexes, palladium complexes, iridium complexes, platinum complexes, and the like.
Examples of rhodium complexes include chlorotris (triphenylphosphine) rhodium, acetylacetonatobis (ethylene) rhodium, acetylacetonatobis (cyclooctene) rhodium, acetylacetonato (1,5-cyclooctadiene) rhodium, 5-cyclooctadiene) bis (triphenylphosphine) rhodium hexafluorophosphate, (norbornadiene) tris (triphenylphosphine) rhodium hexafluorophosphate, bis (1,5-cyclooctadiene) rhodium trifluoromethanesulfonate, bis (norbornadiene) Rhodium tetrafluoroborate, chlorobis (ethylene) rhodium dimer, chlorobis (cyclooctene) rhodium dimer, chloro (1,5-cyclooctadiene) Ethidium dimer, chloro (norbornadiene) rhodium dimer, chloro (dicyclopentadienyl) rhodium dimer, chloro (tetrafluorobenzoylene Bale Ren) rhodium dimer and the like.
Examples of the palladium complex include dichloro (1,5-cyclooctadiene) palladium.
Examples of iridium complexes include acetylacetonato (1,5-cyclooctadiene) iridium, bis (1,5-cyclooctadiene) iridium tetrafluoroborate, chlorobis (cyclooctene) iridium dimer, chloro (1,5-cycloocta Diene) iridium dimer and the like.
Examples of the platinum complex include dichloro (1,5-cyclooctadiene) platinum and dichloro (dicyclopentadienyl) platinum.
Among these, chloro (1,5-cyclooctadiene) rhodium dimer, chloro (norbornadiene) rhodium dimer, and chloro (tetrafluorobenzovalerene) rhodium dimer are preferable. From the viewpoint of polymerization activity and industrial availability, chloro ( Norbornadiene) rhodium dimer is more preferred.

The amount of the group 8-10 metal compound used is preferably in the range of 0.000001 to 10 mol in terms of metal atom per liter of the reaction (polymerization) mixed solution (substituted acetylene and organic solvent described later). The range of 0.0001 to 1 mol is more preferable. When the amount of the group 8-10 metal compound used is less than 0.000001 mol per liter of the reaction (polymerization) mixture in terms of metal atoms, the reaction rate tends to be extremely slow, and exceeds 10 mol. However, an effect commensurate with that cannot be obtained, and the catalyst cost only increases.
Step 1 is carried out in order to increase the activity of the reaction, if necessary, triethylamine, tributylamine, tri-n-octylamine, N, N, N ′, N′-tetramethyl-1,2-diaminoethane, N , N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,4-diaminobutane, N, N-diethylethanolamine, triethanolamine , N-methylpiperidine, N-methylpyrrolidine, N-methylmorpholine, pyridine, picoline, lutidine, collidine, quinoline and the like. When using this additive, it is preferable that the usage-amount is normally 1 mol or more with respect to 1 mol of metals of a group 8-10 metal compound, and can also be used as an organic solvent for reaction.

<Step 1 [polymerization (reaction) conditions]>
The reaction in step 1 is usually performed in an organic solvent. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, isopentyl alcohol, and neopentyl alcohol; (mono, di, tri) methylamine, (same) ethylamine, (same) propylamine, ( The same) alkylamines such as butylamine; amino alcohols such as ethanolamine; dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, butyl methyl ether, tert-butyl methyl ether, dibutyl ether, ethyl phenyl ether, diphenyl ether, tetrahydrofuran , Ethers such as 1,4-dioxane; acetone, ethyl methyl ketone, methyl propyl ketone, diethyl ketone, ethyl propyl ketone, dipro Ketones such as ruketone; hydrocarbons such as heptane, pentane, hexane, octane, cyclohexane; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1-dichloroethane, trichloroethane, chlorobenzene; Nitriles such as acetonitrile, propionitrile and benzonitrile; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and ethylbenzene.
Among these organic solvents, it is preferable to use a highly polar organic solvent such as alcohol, amine and amino alcohol from the viewpoint of reaction rate.
These organic solvents may be used alone or in combination of two or more. When the organic solvent is used, the amount of the organic solvent used is not particularly limited, but is usually 1 to 95% by mass, preferably 70 to 95% by mass in the whole mixed solution of the substituted acetylene and the organic solvent. .
When the amount of the organic solvent used is 1% by mass or more, the viscosity of the mixed solution is lowered to enable efficient stirring, and when the amount is 95% by mass or less, a practical reaction rate is maintained. be able to.
The reaction temperature in step 1 is preferably in the range of −60 to 100 ° C., and more preferably in the range of 0 to 40 ° C.
By setting the reaction temperature to −60 ° C. or higher, the reaction proceeds within an appropriate time, and by setting it to 100 ° C. or lower, side reactions such as isomerization from cis type to trans type can be suppressed.
The reaction time in Step 1 is usually in the range of 1 minute to 20 hours, and preferably in the range of 0.5 to 10 hours. Usually, it is preferable to carry out the reaction for a long time when the reaction temperature is low and for a short time when the temperature is high.
The reaction pressure in step 1 is usually carried out under normal pressure.
Usually, the reaction is carried out according to the following procedure.
First, a mixed solution 1 in which substituted acetylene is dissolved in an organic solvent is prepared. Separately, a mixed liquid 2 in which an additive such as a group 8-10 metal compound and triethylamine as a catalyst is dissolved in the same organic solvent is prepared. Next, the mixed liquid 1 and the mixed liquid 2 are mixed, and stirred while being kept at a predetermined reaction temperature and reacted for a predetermined time, whereby a reaction liquid containing a ct-type substituted acetylene polymer is obtained.

<Step 1 (Polymer Isolation / Purification Method)>
The ct-type substituted acetylene polymer can be isolated and purified from the reaction solution obtained in step 1 by a general method. That is, the obtained reaction solution is added to a poor solvent such as methanol and water to precipitate a polymer, separated by filtration, and then dried to obtain a ct-type substituted acetylene as a raw material in step 2 described below. A polymer can be obtained. If necessary, the polymer can be subjected to a reprecipitation treatment, or a remaining solvent can be removed using a poor solvent and a Soxhlet extractor.

<Step 2 (Shape of ct-type substituted acetylene polymer)>
The shape of the ct-type substituted acetylene polymer used in Step 2 is a block, powder or thin film. From the viewpoint of the processing efficiency from the ct-type substituted acetylene polymer to the cc-type substituted acetylene polymer, that is, from the viewpoint of efficiently absorbing heat, the larger the surface area, the more advantageous. preferable.

<Step 2 (heat treatment)>
In step 2, the ct-type substituted acetylene polymer is isomerized into a cc-type substituted acetylene polymer by heat treatment. A preferable heat treatment temperature is 50 to 100 ° C. By setting the temperature to 50 ° C. or higher, the isomerization efficiency from the ct type to the cc type is prevented from decreasing, and by setting the temperature to 100 ° C. or lower, the crystal part melts and isomerizes from the cis type to the trans type. To prevent.

<Step 2 (treatment technique)>
As a specific treatment method in Step 2, the ct-type substituted acetylene polymer is exposed to hot air under either an inert gas atmosphere or an air atmosphere, or a ct-type substituted acetylene is placed in a sealed container. Preferably, the polymer is added and the container is heated to a predetermined temperature.
For example, when the ct-type substituted acetylene polymer is in the form of powder, the polymer powder may be sprayed from the top under heating with an inert gas or air in the tower, or the powder or granular form is deposited. An inert gas or hot air of air may be circulated in the air. When processing in a film form, you may distribute | circulate an inert gas or the hot air of air in the state wound with the net-like spacer.

<Step 2 (processing conditions)>
The heat treatment time in step 2 is preferably in the range of 1 second to 20 hours, and more preferably in the range of 1 minute to 10 hours. In general, heat treatment is preferably performed in a short time when the temperature is high, and over a long time when the temperature is low.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, measuring instruments and measuring methods used in the following examples and comparative examples are shown.

(1) Molecular structure of substituted acetylene polymer
¹ H-NMR (nuclear magnetic resonance) measurement was performed, and the structure was identified from the chemical shift value when tetramethylsilane was used as an internal standard substance.
<Analysis conditions>
Apparatus: JNM-A400II manufactured by JEOL Ltd.
Solvent: Deuterated chloroform concentration: 20 mg / 0.6 ml
Temperature: 23 ° C
Accumulation count: 32 times (2) The number average molecular weight of the substituted acetylene polymer was measured using gel permeation chromatography (GPC), and was calculated as the polystyrene equivalent molecular weight. Details of the measurement conditions are shown below.
<Analysis conditions>
Apparatus: JASCO Corporation GPC-900
Column: Two K-806L (Shodex) connected (column temperature: 40 ° C.)
Mobile phase: chloroform (flow rate: 1.0 ml / min)
Analysis time: 30 minutes Detector: RI
Filtration: Precision filter concentration with a pore size of 0.45 μm: 3 mg / ml
Injection volume: 20 μl
Sample: Polystyrene analysis: 807-IT integrator manufactured by JASCO (3) Crystal structure of substituted acetylene polymer Using an X-ray diffractometer, a diffraction angle (2θ) = 2 to 35 ° is scanned at a scanning speed of 0.6 °. / Min and measured by symmetric reflection method (WAXD analysis). Details of the measurement conditions are shown below.
<Analysis conditions>
Apparatus: RINT2200 manufactured by Rigaku Corporation
X-ray generator: enclosed tube X-ray generator X-ray source: Cu 40 kV 40 mA
Goniometer: Sample horizontal goniometer Detector: Scintillation counter Step width: 0.04 °
Slit: Divergent slit = 1 °, Light receiving slit = 0.15 mm, Scattering slit = 1 °
Collimator: None Sample: Filled in platinum cell (4) Conformational analysis of substituted acetylene polymer The structure optimization of substituted acetylene icomers was performed by changing the dihedral angle using molecular force field method. The obtained local stable structures were cc type and ct type, respectively, and the length of the crystal axis of the crystal was calculated from the molecular size at that time. Details of the calculation conditions are shown below.
<Calculation conditions>
Software used: Spartan '04 Windows ver. 1.03
Force field: MMFF94
Hereinafter, a specific procedure will be described by taking 4-butoxyphenylacetylene as an example.
(a) A 20-mer of 4-butoxyphenylacetylene was drawn so that the dihedral angle of the main chain double bond was 180 °, and the terminal was hydrogen.
(b) The structure was optimized using the molecular force field method with the dihedral angle of 170 ° and the dihedral angle fixed, and the energy of the stabilized structure was obtained.
(c) Subsequently, the dihedral angle of the model obtained in (b) above was changed to 160 °, and the structure was optimized using the molecular force field method with the dihedral angle fixed, thereby stabilizing the structure. Gained energy.
(d) Similarly, the energy of the stabilizing structure at each dihedral angle was obtained by repeating the process every 10 ° until the dihedral angle reached 40 °.
(e) The relationship between the dihedral angle and the energy of the stabilized structure [strain energy (kcal / mol)] at each dihedral angle was plotted, and minimum values were obtained at 70 ° and 120 ° (see FIG. 1).
In FIG. 1, the vertical axis represents the energy of the stabilizing structure, and the horizontal axis represents the dihedral angle φ (°).
(f) The structure having a dihedral angle of 70 ° was cc type, and the structure having a 120 ° angle was ct type, and the length of the crystal axis of the crystal was calculated from the molecular size.
(5) ESR (spin density) measuring device name of heated sample: JEOL FE1XG
Measurement conditions: Magnetic field 3360 ± 100G
MODULATION 4G
Microwave Power 0.4mW
Measurement temperature: room temperature Sample: 50 mg of a sample was put into a 5 mm ESR sample tube, connected to a vacuum line, degassed at 10 ⁻³ torr for 2 hours, and sealed. After the measurement at room temperature, the sample tube was immersed in an oil bath at 140 ° C. for 1 hour and then cooled to room temperature.

[Synthesis Example 1 Synthesis 1 of Substituted Acetylene Polymer]
A U-shaped glass tube having a diameter (inner diameter) of 20 mmφ and a straight-line conversion length of 200 mm was placed with both ends opened downward, and dissolved in 7.2 ml of ethanol dried from one of the openings 4- ( 13.4 mg (0.029 mmol) of chloro (norbornadiene) rhodium dimer and triethylamine dissolved in 7.2 ml of ethanol dried from the opening side on the other side of a solution of 667 mg (2.9 mmol) of n-octyloxy) phenylacetylene 0.4 ml of each solution was added, and both solutions were mixed by inversion so that the opening portions on both ends of the U-shaped glass tube faced upward, and the reaction was started. The reaction was carried out at 20 ° C. for 2 hours.

Subsequently, excess methanol was added to stop the reaction, and the precipitated yellow polymer was filtered, washed with methanol, and then vacuum-dried for 12 hours. As a result of ¹ H-NMR analysis of the obtained polymer, peaks were observed at σ (ppm) = 6.58, 6.43, 5.74, 3.66, 1.66, 1.28, 0.88. It was confirmed that it was 4- (n-octyloxy) phenylacetylene polymer which is a polymer of substituted acetylene. Moreover, the number average molecular weight of the obtained polymer was 159,000. Subsequently, WAXD analysis was performed. The results are shown in FIG. When it is assumed that the diffraction peak appearing at the interplanar spacing d = 24.0Å (2θ = 3.681 °) belongs to the (100) plane of the hexagonal crystal, the relational expression between the interplanar spacing d and the lattice constant
1 / d ² = 4 (h ² + hk + k ² ) / 3a ² + l ² / c ²
a, c: Crystal axis length: [Å]
h, k, l: Miller index: [-]
From this, a = 27.7２７ is obtained. Similarly, when it is assumed that the diffraction peak appearing at the interplanar spacing d = 12.1Å (2θ = 7.306 °) belongs to the (200) plane of hexagonal crystal, a / 2 = 14.0Å is obtained. Since the surface was equivalent to the diffraction peak that appeared at an interplanar spacing d = 24.0 mm (2θ = 3.681 °), the crystal structure of the obtained polymer was assigned to be a pseudohexagonal crystal. The value of a obtained from the WAXD analysis was calculated by the molecular force field method on the assumption that the 4- (n-octyloxy) phenylacetylene polymer is ct type and the crystal structure is a pseudo hexagonal crystal. Since the value almost coincided with 27.9%, the obtained polymer was assigned to be ct type.

[Synthesis Example 2 Synthesis 2 of Substituted Acetylene Polymer]
The reaction was performed in the same manner as in Synthesis Example 1 except that 626 mg (2.9 mmol) of 4- (n-heptyloxy) phenylacetylene was used instead of 4- (n-octyloxy) phenylacetylene in Synthesis Example 1. As a result of ¹ H-NMR analysis of the obtained polymer, peaks were observed at σ (ppm) = 6.58, 6.44, 5.74, 3.67, 1.65, 1.31, 0.89. It was confirmed that it was 4- (n-heptyloxy) phenylacetylene polymer which is a polymer of substituted acetylene. Moreover, the number average molecular weight of the obtained polymer was 184,000. Subsequently, WAXD analysis was performed. The results are shown in FIG. When it is assumed that the diffraction peak appearing at the interplanar spacing d = 23.8Å (2θ = 3.712 °) belongs to the (100) plane of the hexagonal crystal, the relational expression between the interplanar spacing d and the lattice constant
1 / d ² = 4 (h ² + hk + k ² ) / 3a ² + l ² / c ²
a, c: Crystal axis length: [Å]
h, k, l: Miller index: [-]
From this, a = 27.4２７ is obtained. Similarly, when it is assumed that the diffraction peak appearing at the interplanar spacing d = 11.8Å (2θ = 7.492 °) belongs to the (200) plane of hexagonal crystal, a / 2 = 13.7Å is obtained. Since the surface was equivalent to the diffraction peak that appeared at an interplanar spacing of d = 23.8 mm (2θ = 3.712 °), the crystal structure of the obtained polymer was assigned to be a pseudo hexagonal crystal. The value of a obtained from the WAXD analysis was calculated by the molecular force field method assuming that 4- (n-heptyloxy) phenylacetylene polymer is ct type and its crystal structure is pseudo hexagonal. Since the value almost coincided with 27.4%, the obtained polymer was assigned to be ct type.

[Example 1]
150 mg of the powdery ct-type 4- (n-octyloxy) phenylacetylene polymer obtained in Synthesis Example 1 was heated from 30 ° C. to 100 ° C. at a rate of 10 ° C./hour. Hold for a minute.
FIG. 4 shows the results of WAXD analysis after the heat treatment. When it is assumed that the diffraction peak appearing at the interplanar spacing d = 28.2Å (2θ = 3.133 °) belongs to the hexagonal (100) plane, the relational expression between the interplanar spacing d and the lattice constant
1 / d ² = 4 (h ² + hk + k ² ) / 3a ² + l ² / c ²
a, c: length of crystal axis [Å]
h, k, l: Miller index [-]
From this, a = 32.6 Å is obtained. Similarly, when it is assumed that the diffraction peak appearing at the interplanar spacing d = 14.1 Å (2θ = 6.268 °) belongs to the (200) plane of hexagonal crystal, a / 2 = 16.3 Å is obtained. Since the surface was equivalent to the diffraction peak that appeared at an interplanar spacing d = 28.2． (2θ = 3.133 °), the crystal structure of the obtained polymer was assigned to be a pseudo hexagonal crystal.
The value of a obtained from the WAXD analysis was calculated by the molecular force field method assuming that the 4- (n-octyloxy) phenylacetylene polymer is cc type and the crystal structure is pseudo hexagonal. Since it almost coincided with the value 32.8Å, it was attributed that the structure was changed from ct type to cc type by heat treatment.
The obtained polymer had a spin density of 5.5 × 10 ¹⁵ (spins / g).

[Example 2]
150 mg of the powdery 4- (n-heptyloxy) phenylacetylene polymer obtained in Synthesis Example 2 is heat-treated while being heated from 30 ° C. to 90 ° C. at 10 ° C./hour, and kept at 90 ° C. for 10 minutes. did. FIG. 5 shows the results of WAXD analysis after the ct type heat treatment. When it is assumed that the diffraction peak appearing at the interplanar spacing d = 27.6Å (2θ = 3.201 °) belongs to the (100) plane of the hexagonal crystal, the relational expression between the interplanar spacing d and the lattice constant
1 / d ² = 4 (h ² + hk + k ² ) / 3a ² + l ² / c ²
a, c: length of crystal axis [Å]
h, k, l: Miller index [-]
From this, a = 31.9Å is obtained. Similarly, when it is assumed that the diffraction peak appearing at the interplanar spacing d = 13.6Å (2θ = 6.499 °) belongs to the (200) plane of hexagonal crystal, a / 2 = 15.7Å is obtained. Since the surface was equivalent to the diffraction peak that appeared at an interplanar spacing d = 27.6 mm (2θ = 3.201 °), the crystal structure of the obtained polymer was assigned to be a pseudo hexagonal crystal.
The value of a obtained from the WAXD analysis was calculated by the molecular force field method assuming that the 4- (n-heptyloxy) phenylacetylene polymer is cc type and the crystal structure is pseudo hexagonal. Since it almost coincided with the value of 31.6%, it was attributed that the structure was changed from ct type to cc type by heat treatment.
Moreover, the spin density of the obtained polymer was 6.3 × 10 ¹⁵ (spins / g).

[Comparative Example 1]
150 mg of the powdery ct-type 4- (n-octyloxy) phenylacetylene polymer obtained in Synthesis Example 1 was heated from 30 ° C. to 140 ° C. at a rate of 10 ° C./hour. Hold for a minute.
FIG. 6 shows the results of WAXD analysis after the heat treatment. It is clear that the crystalline peak disappears and the crystal part is melted. Further, the spin density of the obtained polymer is 7.2 × 10 ¹⁷ (spins / g), the spin density is clearly increased as compared with Example 1, and the isomerization to the trans type is observed. It is clear that it is progressing.

[Comparative Example 2]
As a substituted acetylene polymer, 150 mg of the ct-type 4- (n-heptyloxy) phenylacetylene polymer obtained in Synthesis Example 2 was heated from 30 ° C. to 130 ° C. at a rate of 10 ° C./hour, and subjected to a heat treatment at 130 ° C. For 10 minutes. FIG. 7 shows the results of WAXD analysis after the heat treatment. It is clear that the crystalline peak disappears and the crystal part is melted.
In addition, the obtained polymer has a spin density of 8.7 × 10 ¹⁷ (spins / g), and the spin density is clearly increased as compared with Example 2. It is clear that it is progressing.

[Comparative Example 3]
150 mg of the powdery ct-type 4- (n-octyloxy) phenylacetylene polymer obtained in Synthesis Example 1 is heated from 30 ° C. to 40 ° C. at a rate of 10 ° C./hour, and heated at 40 ° C. Hold for a minute. FIG. 8 shows the results of WAXD analysis after the heat treatment. From the comparison with FIG. 4, it is clear that no structural change has occurred before and after the heat treatment.

[Comparative Example 4]
150 mg of the powdery ct-type 4- (n-heptyloxy) phenylacetylene polymer obtained in Synthesis Example 2 was heat-treated while being heated from 30 ° C. to 40 ° C. at 10 ° C./hour. Hold for a minute. FIG. 9 shows the results of WAXD analysis after the heat treatment. From the comparison with FIG. 5, it is clear that the structural change does not occur before and after the heat treatment.

[Comparative Example 5]
In Synthesis Example 1, the reaction was carried out in the same manner except that the amount of chloro (norbornadiene) rhodium dimer used was 1.34 mg (2.9 μmol) and the polymerization solvents were ethanol and hexane, respectively. FIG. 10 shows the change over time in the conversion rate of 4-octyloxyphenylacetylene, which is a monomer. From FIG. 10, when the amount of the expensive rhodium complex used in the polymerization reaction is reduced, the resulting polymer is ct type, but the consumption rate of the monomer is clearly faster in ethanol, and in the hexane solvent according to Non-Patent Document 1. It can be seen that the polymerization proceeds more efficiently than the direct polymerization to cc type.

The cc-type substituted acetylene polymer obtained by the production method of the present invention is suitable for highly functional materials such as conductive materials, electroluminescence materials, electromagnetic wave shielding materials, and gas adsorbents.

It is the graph which plotted the relationship of the energy of the stabilization structure in a dihedral angle and each dihedral angle for the conformational analysis of a substituted acetylene polymer. It is a WAXD analysis result performed in order to confirm that the 4- (n-octyloxy) phenyl acetylene polymer obtained by the synthesis example 1 is ct type. It is a WAXD analysis result performed in order to confirm that the 4- (n-heptyloxy) phenylacetylene polymer obtained in Synthesis Example 2 was a ct type. 3 is a WAXD analysis result of 4- (n-octyloxy) phenylacetylene polymer heat-treated at 100 ° C. in Example 1. FIG. 4 is a WAXD analysis result of 4- (n-heptyloxy) phenylacetylene polymer heat-treated at 90 ° C. in Example 2. FIG. 4 is a WAXD analysis result of a ct-type 4- (n-octyloxy) phenylacetylene polymer heat-treated at 140 ° C. in Comparative Example 1. 4 is a result of WAXD analysis of a ct-type 4- (n-heptyloxy) phenylacetylene polymer heat-treated at 130 ° C. in Comparative Example 2. It is a WAXD analysis result of the ct type | mold 4- (n-octyloxy) phenylacetylene polymer heat-processed at 40 degreeC in the comparative example 3. It is a WAXD analysis result of the ct type | mold 4- (n-heptyloxy) phenylacetylene polymer heat-processed at 40 degreeC in the comparative example 4. 6 is a graph showing the change over time in the conversion rate of 4- (n-octyloxy) phenylacetylene in Comparative Example 5. FIG.

Claims (3)

Formula (I)

[Wherein n is an integer of 10 to 100,000. R represents 4- (n-octyloxy) phenyl group or 4- (n-heptyloxy) phenyl group]
A process for producing a cis-cisoid substituted acetylene polymer, comprising heat-treating a powdered cis-transoid substituted acetylene polymer represented by the formula: The powdery cis-transoid type substituted acetylene polymer has the general formula (II)

[Wherein, R represents the same group as in the general formula (I)]
The method for producing a cis-cisoid type substituted acetylene polymer according to claim 1, which is an acetylene polymer obtained by polymerizing a substituted acetylene represented by formula (8) in the presence of a group 8-10 metal compound.   In the heat treatment, the cis-transoid substituted acetylene polymer is exposed to hot air under either an inert gas atmosphere or an air atmosphere, or the cis-transoid substitute is placed in a sealed container. The method for producing a cis-cisoid substituted acetylene polymer according to claim 1 or 2, wherein the acetylene polymer is added and the container is heated to a predetermined temperature.

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