JP2005248165A - Acetylene polymer and process for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high molecular weight acetylene polymer obtained by using industrially inexpensive raw materials and a method for producing the same.
[MEANS FOR SOLVING PROBLEMS] A method for producing an acetylene polymer in which a propargyl alcohol derivative is polymerized in the presence of an organometallic complex, and an acetylene polymer obtained by the production method. The organometallic complex is preferably a complex composed of a 7-10 group element. The propargyl derivative is preferably an ester compound, an ether compound, or a urethane compound. The obtained acetylene polymer is preferably a polymer having a mass average molecular weight of 5600 or more and a dispersity of 1-30.
[Selection figure] None

Description

  The present invention relates to an acetylene polymer and a method for producing the same.

Conventionally, for example, acetylene, alkylacetylene, phenylacetylene in the presence of a catalyst such as a Ziegler-Natta catalyst such as Ti compound / organoaluminum, iron complex / organoaluminum, a metathesis catalyst such as molybdenum or tungsten, or a rhodium complex catalyst. A method for producing an acetylene polymer by polymerizing an acetylene compound such as the above is known (see, for example, Patent Documents 1 to 3).
On the other hand, an attempt to obtain a polymer by polymerizing propargyl alcohol at a low price among acetylene compounds is known (see, for example, Non-Patent Document 1).
JP 59-210914 A JP-A-63-277212 JP-A 63-275613 A. Furlani et al. , Polymer, 38, 1, 183-189, 1997.

The acetylene-based polymer has been developed for use in electric materials and pharmaceutical materials because of its excellent characteristics. However, as described in Patent Documents 1 to 3, conventionally known acetylene-based compounds are Since it is gaseous at room temperature, it is complicated to obtain a polymer by polymerizing industrially, or the range of use is limited industrially because the price of the acetylene compound is expensive is the current situation.
Propargyl alcohol is a relatively inexpensive and easy-to-handle compound among acetylene compounds, and there is an attempt to polymerize this to obtain an acetylene polymer, but a polymer obtained by polymerizing propargyl alcohol. Has low stereoregularity, and a high molecular weight polymer has not been obtained (see, for example, Non-Patent Document 1). Thus, a high molecular weight polymer of propargyl alcohol or its derivative is not yet known.
An object of the present invention is to provide a high-molecular-weight acetylene polymer obtained by using industrially inexpensive raw materials that are easy to handle and a method for producing the same.

  As a result of intensive studies, the inventor is inexpensive as a raw material, but has low stereoregularity even when polymerized, and instead of propargyl alcohol that gives only a low molecular weight polymer such as an oligomer, for example, its ester, ether, Alternatively, the inventors have found that by using a propargyl alcohol derivative such as a urethane derivative as a raw material, a polymer having a high polymerization yield and a high stereoregularity can be obtained, and the present invention has been achieved.

That is, the method for producing an acetylene polymer of the present invention is characterized in that a propargyl alcohol derivative is polymerized in the presence of an organometallic complex.
In the method for producing an acetylene polymer of the present invention, the organometallic complex is preferably a compound represented by the following general formula (I).
[ML _m L ′ _n ] _p X _q (I)
(Wherein, M is a group 7-10 element, L is a ligand derived from a compound having multiple bonds, L ′ is a ligand derived from a compound having a lone pair, X is an anion, m is (An integer of 0-7, n is an integer of 0-6, p is an integer of 1-2, q represents an integer of 0-2.)
In the method for producing an acetylene polymer of the present invention, the propargyl alcohol derivative is preferably an ester compound represented by any one of the following general formulas (II) to (IV).
CH≡C—CH ₂ —OCO—X ¹ (II)
(In the formula, X ¹ represents a hydrogen atom or an organic group.)
CH≡C—CH ₂ —O—X ² (III)
(In the formula, X ² represents an organic group.)
CH≡C—CH ₂ —OCONH-X ³ (IV)
(In the formula, X ³ represents an organic group.)
The acetylene polymer of the present invention is obtained by the above production method.
In the acetylene polymer of the present invention, the mass average molecular weight (Mw) is preferably 5600 or more, and the dispersity (Mw / Mn) is preferably 1 to 30.

  In the present invention, a derivative using inexpensive propargyl alcohol as a starting material is used, and a polymer obtained by polymerizing this propargyl alcohol derivative is industrially easy to handle, can be produced at low cost, and has a high yield. A polymer having a large molecular weight and high stereoregularity can be obtained. These polymers are useful for various electrical and electronic materials and pharmaceutical materials.

Hereinafter, the present invention will be described in detail.
The organometallic complex used in the method for producing an acetylene polymer of the present invention includes the following general formula (I):
[ML _m L ′ _n ] _p X _q (I)
(Wherein, M is a group 7-10 element, L is a ligand derived from a compound having multiple bonds, L ′ is a ligand derived from a compound having a lone pair, X is an anion, m is An integer of 0 to 7, n is an integer of 0 to 6, p is an integer of 1 to 2, and q is an integer of 0 to 2). By using the organometallic complex represented by the above general formula (I) as a catalyst, a polymer having high stereoregularity can be obtained.

As M in the general formula (I), rhodium, ruthenium, rhenium, nickel, platinum, palladium, iridium and the like are preferable, and rhodium is particularly preferable.
In general formula (I), L represents a ligand derived from a compound having multiple bonds. The compound having multiple bonds is preferably olefin, acetylene, diene, cycloolefin, carbon monoxide, phenylacetylene, etc., particularly preferably cycloolefin, propylene (allyl group as a ligand), carbon monoxide. , Phenylacetylene and the like, more preferably cycloolefin. As the cycloolefin, cyclooctadiene or norbornadiene is preferably used.

In the general formula (I), L ′ represents a ligand derived from a compound having a lone electron pair.
As the compound having a lone electron pair, a ligand having an atom such as nitrogen, phosphorus, arsenic, oxygen, or sulfur, or a halogen atom is preferably used. Particularly preferred are phosphorus-containing ligands and halogen atoms, and most preferred are halogen atoms.
Specifically, as a ligand having nitrogen, for example, pyridine, bipyridyl, ethylenediamine, triethylenediamine, triethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [ 2.2.2] octane, phenanthroline and the like. Examples of the compound having phosphorus include triphenylphosphine, trioctylphosphine, triphenylphosphite, triphenylphosphate, bisdiphenylphosphine, n-nonylphenylphosphine, ethylenebisphenylphosphine, and triphenylphosphine is particularly preferable. Examples of the arsenic-containing ligand include triphenylarsine. Examples of the ligand having oxygen include diphenyl ether and alkoxy. Examples of the ligand having sulfur include diphenylthioether. Examples of the halogen atom include chlorine, bromine and iodine, and chlorine is particularly preferable.

In general formula (I), X represents an anion. Specific examples of X include PF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , SO ₃ CF ₃ ^{— and the} like, and PF ₆ ⁻ is preferably used.
In the general formula (I), m represents an integer of 0 to 7, preferably an integer of 0 to 6, particularly preferably an integer of 1 to 2. n represents an integer of 0-6, preferably an integer of 0-5, particularly preferably an integer of 1-2. p represents an integer of 1 to 2; q represents an integer of 0 to 2, preferably an integer of 1 to 2, and most preferably 2.

Specific examples of the organometallic complex represented by the general formula (I) include [Rh (COD) Cl] ₂ , [Rh (NBD) Cl] ₂ , [Rh (NBD) OCH ₃ ] ₂ , [Rh (COD). ) bipy] SO ₃ CF ₃ , [Rh (COD) bipy] PF ₆ , [Rh (NBD) bipy] PF ₆ , [Rh (COD) bipyam] PF ₆ , [Rh (COD) (PPh ₃ ) ₂ ] PF ₆ , [Rh (COD) EDA] Cl, [Rh (COD) TEDA] Cl, Re (CO) ₅ Z, [Re (CO) ₂ Cl] ₂ , [Re (CO) ₄ Cl] ₂ , Re (CO ) ₄ (PPh ₃ ) Cl, Re (CO) ₃ (PPh ₃ ) ₃ Cl, Re (CO) ₃ (bipy) Cl, Re (CO) ₅ (C≡CPh), Re (CO) ₃ (Ph ₂ PCH _{2 CH 2 PPh 2) Cl,} Ni (CO) 2 (PPh 3) 2, Ni (PPh 3) 2 Z 2, Pt (PPh 3) 3 (C≡CPh) 2, P (PPh ₃₎ HCl, etc. Pt (PPh _{3) 3} Cl ₂ and the like. However, COD is cyclooctadienyl, NBD is norbonadienyl, bipy is bipyridyl, bipyam is bipyran, Ph is phenyl, EDA is ethylenediamine, TEDA is triethylenediamine, and Z is a halogen atom.
Among them, rhodium metal complexes such as [Rh (COD) Cl] ₂ , [Rh (NBD) Cl] ₂ , and [Rh (NBD) OCH ₃ ] ₂ have high stereoregularity as organometallic complexes used in the present invention. From the viewpoint of giving a high molecular weight polymer, [Rh (NBD) Cl] ₂ is particularly preferable.

An example is given and demonstrated about the propargyl alcohol derivative in this invention.
In the present invention, the propargyl alcohol derivative is a derivative derived from propargyl alcohol and does not include propargyl alcohol itself.
As propargyl alcohol derivatives, the following general formula (V)
CH≡C—CH ₂ —Z (V)
A compound bonded with propargyl alcohol as represented by an ester bond, an ether bond or a urethane bond is preferably used because it is easy to synthesize and gives a high molecular weight polymer, but is not limited to these compounds. Absent.
In the above general formula (V), ^-Z is ^{-OCO-X 1, -O-X} 2, represents either ^{-OCONH-X 3} (see above general formula (II) ~ (IV)) .

A propargyl alcohol derivative having an ester bond in which —Z is represented by —OCO—X ¹ will be described.
X ¹ represents a hydrogen atom or an organic group. The organic group is not specified and may be any organic group and may have any substituent. When X ¹ is an organic group, specific examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a sulfo group. This compound can be obtained by reaction of propargyl alcohol with an organic acid, or in some cases, an organic acid anhydride or an organic acid halide thereof. The organic acid includes a saturated and / or unsaturated carboxylic acid compound which may be unsubstituted or substituted, and may have an asymmetric carbon. Specifically, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, lauric acid, palmitic acid, stearic acid, phenylacetic acid, oxalic acid, fumaric acid, phthalic acid, maleic acid, malonic acid , Propiolic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, trifluoroacetic acid, p-phenolsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and organic acids having an aryl group include benzoic acid Acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, 1-naphthalenecarboxylic acid, 9-anthracenecarboxylic acid, 1-pyrenecarboxylic acid, 1-pyreneacetic acid, 1-pyrenebutyric acid, etc. Ku substitution positions may be different naphthalene, anthracene, pyrene, carboxylic acids such as the grant phenanthrene, acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid and the like.

  Examples of the organic acid having an asymmetric carbon include racemic hydroxycarboxylic acids such as tartaric acid, malic acid, lactic acid, mandelic acid, dibenzoyltartaric acid, citramalic acid, phenyllactic acid, and 1,4-benzodioxan-2-carboxylic acid. Its derivatives, 2-bromopropionic acid, γ-carboxy-γ-butyrolactone, 2-chlorobutanoic acid, 2-methylhexanoic acid, 2-methyldecanoic acid, 2-methylbutanoic acid, menthyloxyacetic acid, tetrahydrofuran acid, 2-phenylbutanoic acid, 2-phenylpropionic acid, 2-phenylsuccinic acid, N-substituted amino acid, pyroglutamic acid, camphoric acid, 10-camphorsulfonic acid, phenylethanesulfonic acid, α-bromocamphor-π-sulfonic acid, 3-endobromocamphor- 8-sulfonic acid, 1-amino-2- Etc. chill propyl phosphonic acid.

  These ester compounds are used in normal esterification reaction conditions, for example, in a solvent or in the absence of a solvent, if necessary, under an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid, or when an acid anhydride or acid halide is used. It can be obtained by reacting under a base catalyst such as pyridine or triethylamine.

Next, a propargyl alcohol derivative having an ether bond in which —Z is represented by —O—X ² will be described. Here, ^{X 2} represents an organic group. The organic group is not particularly specified, and may be any organic group and may have any substituent. Specific examples of X ² include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a cycloalkyl group, and the like, and may have an asymmetric carbon. This compound can be obtained, for example, by reacting propargyl alcohol with an organic halide. The organic halide may be a saturated or unsaturated alkyl halide, aromatic halide, or alicyclic halide, and chlorine, bromine, iodine, fluorine, or the like can be used as the halogen. Specific examples of the alkyl halide include methyl bromide, ethyl bromide, propyl bromide, butyl bromide, hexyl bromide, octyl bromide, decyl bromide, 2-bromopropane, 2-bromopentane, 3 -Alkyl bromide having an ether bond, such as linear or branched alkyl bromide such as bromopentane, 2-bromoethyl ethyl ether, 2-bromo-1,1-dimethoxyethane, 2-bromomethyldioxolane Alkyl bromide having an unsaturated bond such as allyl bromide, 4-bromo-1-butene, 3-bromo-1-propyne, 1-bromoacetonitrile, 4-bromobutyronitrile, and chlorides instead of the bromides And iodide.

Examples of the aromatic halide include alkyl-substituted bromobenzene such as bromobenzene and p-methylbromobenzene, alkoxy-substituted bromobenzene such as p-methoxybromobenzene, p-nitrobromobenzene, benzyl bromide, cinnamyl bromide, 2 -Bromoethylphenyl ether, 2-bromomethylnaphthalene, 4-bromobiphenyl, 5-bromopyrimidine, bromonaphthalene, naphthylmethyl bromide, bromoanthracene, anthranylmethyl bromide, bromopyrene, pyrenylmethyl bromide, which may have different substitution positions, Examples thereof include bromofluorene, fluorenylmethyl bromide, chlorides and iodides in place of the bromides.
Examples of the alicyclic halide include organic compounds such as bromocyclopropane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromobicyclo [2.2.1] heptane, bromoadamantane, and chlorides and iodides instead of the bromides. A halide is mentioned.

  These ether compounds are used in the usual etherification reaction conditions, for example, in the presence or absence of a solvent, in the presence of a base such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride, potassium tert-butoxy and the like. If necessary, it can be obtained by adding a metal catalyst such as a copper catalyst and reacting propargyl alcohol with an organic halide.

Next, a propargyl alcohol derivative having a urethane bond in which -Z is represented by -OCONH-X ³ will be described.
Here, X ³ represents an organic group. The organic group is not particularly specified, and may be any organic group and may have an arbitrary substituent. Specific examples of X ³ include an alkyl group, an aryl group, a cycloalkyl group, and the like, and may have an asymmetric carbon. This compound can be obtained by the reaction of propargyl alcohol and an isocyanate compound. As an isocyanate compound, any of aliphatic isocyanate, aromatic isocyanate, and alicyclic isocyanate may be sufficient.
These isocyanate compounds include monoisocyanate compounds, diisocyanate compounds and polyisocyanate compounds. Specifically, for example, as the monoisocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, methoxypropyl isocyanate, hexyl isocyanate, octyl isocyanate, phenyl isocyanate, benzyl isocyanate, cyclohexyl isocyanate, naphthyl isocyanate and anthranyl which may be substituted at different positions Monoisocyanates such as isocyanate, pyrenyl isocyanate, and fluorenyl isocyanate are listed. Examples of the diisocyanate include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, hydrogenated 4,4. Examples include '-diphenylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, and norbornane diisocyanate. Examples of the isocyanate having an asymmetric carbon include 1-phenylethyl isocyanate and 1-methylpropyl isocyanate. These urethane compounds are usually urethanation reaction conditions, for example, in a solvent or in the absence of a solvent, and if necessary, amine compounds such as triethylamine, triethylenediamine, hexamethylenetetramine, pyridine, organometallic compounds such as dibutyltin dilaurate, lead octoate, etc. It can obtain by reacting in the presence of a urethanization catalyst such as.

  A polymer of a propargyl alcohol derivative can be produced by polymerizing one or more of the propargyl alcohol derivatives as monomers in the presence of an organometallic complex. Further, at the time of polymerization, another acetylene monomer may be added and copolymerized.

Furthermore, a co-catalyst may be added as necessary during the polymerization.
Examples of the cocatalyst include compounds having atoms such as nitrogen, phosphorus, arsenic, oxygen and sulfur. Specifically, as a compound having nitrogen, for example, pyridine, bipyridyl, ethylenediamine, triethylenediamine, triethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2. 2.2] octane, phenanthroline and the like. Examples of the compound having phosphorus include triphenylphosphine, trioctylphosphine, triphenylphosphite, triphenylphosphate, bisdiphenylphosphine, n-nonylphenylphosphine, ethylenebisphenylphosphine, and triphenylphosphine is particularly preferable. . Examples of the compound having arsenic include triphenylarsine. Examples of the compound having oxygen include diphenyl ether and alkoxy. Examples of the compound having sulfur include diphenylthioether.

  Examples of the polymerization method include solution polymerization, suspension polymerization, emulsion polymerization, and gas phase polymerization. The preferred polymerization method varies depending on the use of the polymer, but solution polymerization and emulsion polymerization are preferred when used in the form of a film, and when the polymer is used as a solid, the polymer is taken out from the reaction system after completion of the polymerization. From the viewpoint of easy operation, suspension polymerization is preferred. In solution polymerization, a monomer and a catalyst are dissolved in a solvent and polymerized. In suspension polymerization, a catalyst is added in advance to a solvent in which the monomer is dissolved and the polymer is not dissolved, and then the monomer is added for polymerization, or the monomer is dissolved and the monomer is dissolved in a solvent in which the polymer is not dissolved. After dissolution, the catalyst is added and polymerized. In emulsion polymerization, first, a monomer emulsion is prepared by mixing the monomer, the emulsifier and water, and a catalyst suspension prepared by mixing a catalyst, a dispersant and water separately from this is added to the monomer emulsion. And polymerize. As the solvent used in the polymerization method, a solvent suitable for each polymerization method can be appropriately selected. For example, a solvent such as ethanol, methanol, propanol, diethyl ether, tetrahydrofuran, dioxane, anisole, chloroform, toluene, water or the like. Can react in. In the solution polymerization, a solvent capable of dissolving the monomer and the catalyst can be used. In the suspension polymerization, an alcohol solvent such as methanol, ethanol, propanol or the like in which a polymer precipitates during the polymerization is preferable.

The concentration of the monomer dissolved in such a solvent is preferably 0.01 to 10 mol / L, more preferably 0.1 to 5 mol / L. The catalyst concentration is preferably 1 × 10 ⁻¹⁰ to ¹ mol / L, more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol / L. The amount of catalyst added relative to the amount of monomer is preferably monomer / catalyst = 1 × 10 ¹² to 1 × 10 ⁻² mol / mol, more preferably 5 × 10 ^{5 to} 1 mol / mol. The temperature during the polymerization is preferably -30 to 120 ° C, more preferably 0 to 100 ° C, and particularly preferably 20 to 80 ° C. The pressure is usually carried out at normal pressure, but depending on the type of solvent or propargyl alcohol derivative used, it is carried out under pressurized conditions.
According to the above-described polymerization method, the obtained polymer of the propargyl alcohol derivative is obtained in a high yield, and the obtained polymer is a polymer having a large molecular weight.

  The obtained polymer is purified as necessary. Examples of the purification method include washing with a solvent, purification by a reprecipitation method in which a polymer is dissolved and reprecipitated. By purifying in this way, impurities such as residual monomers and residual organometallic complexes can be reduced. Polymers with few impurities such as residual monomers and residual organometallic complexes can be used as high quality polymers.

  In the acetylene-based polymer (polymer of propargyl alcohol derivative) of the present invention obtained by the production method described above, the mass average molecular weight (Mw) is preferably 5,600 or more, more preferably 5,600 to 5,000. 1,000, particularly preferably 10,000 to 500,000. The degree of dispersion [mass average molecular weight (Mw) / number average molecular weight (Mn)] of the polymer is preferably 1 to 30, more preferably 1 to 20, and particularly preferably 1 to 10. By setting the Mw to 5,600 or more, the polymer of the propargyl alcohol derivative can be easily separated from the polymerization reaction system and the yield is good, and by making the dispersity 1-30, the film-forming property and flexibility of the film Sexuality improves. The molecular weight can be adjusted by selecting conditions such as polymerization temperature and monomer / catalyst ratio, and the degree of dispersion can be adjusted by selecting the type of solvent, monomer and catalyst concentration, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail from an Example, this invention is not limited to a following example, unless the summary is exceeded.
The following synthesis examples 1 to 4 are ester bonds, synthesis example 5 is an ether bond, and synthesis examples 6 and 7 are synthesis examples of a propargyl alcohol derivative having a urethane bond.
Moreover, the analysis of the monomer and the polymer was carried out by IR, ¹ H-NMR and GPC. IR was measured using JIR-5500 manufactured by JEOL. ¹ H-NMR was measured by using JEOL, JNM-ECP400 (400 MHz) and Varian, Gemini-200 (200 MHz), and deuterated chloroform as a solvent. GPC was measured using a Shodex K-806L column manufactured by Showa Denko, using polystyrene as a standard sample and chloroform as a solvent.

(Synthesis Example 1)
Synthesis of acetic acid 2-propynyl ester 10.0 g (178.4 mmol) of propargyl alcohol was reacted with 21.9 g (214.1 mmol) of acetic anhydride in 16.9 g (214.1 mmol) of pyridine for 6 hours. Was purified by distillation under reduced pressure to obtain 15.2 g (yield: 87%) of acetic acid 2-propynyl ester.
Boiling point: 70 ° C. (150 mmHg), IR (neat) 3290 (≡C—H) 2130 (C≡C) 1740 (C═O) cm ⁻¹ , ¹ H-NMR (200 MHz) δ2.12 (s, 3H, _{HC≡CCH 2 OCOC H 3), 2.49} (brt, 1H, H C≡CCH 2 OCOCH 3), 4.68 (brd, 2H, HC≡CC H 2 OCOCH 3)

(Synthesis Example 2)
Synthesis of 1-naphthalenecarboxylic acid 2-propynyl ester 8.0 g (47.7 mmol) of 1-naphthalenecarboxylic acid was reacted in 80.0 g (672.4 mmol) of thionyl chloride at 76 ° C. for 2 hours and concentrated to give excess chloride. Thionyl was distilled off. Subsequently, propargyl alcohol (5.2 g, 93.3 mmol) and pyridine (100 ml) were added and reacted at room temperature for 1 hour. The organic layer was washed with 5% aqueous sodium hydrogen carbonate solution and water, then concentrated, and the resulting product was obtained. Was purified by column chromatography. As a result, 8.5 g (yield: 87%) of 1-naphthalenecarboxylic acid 2-propynyl ester was obtained.
Melting point: 66-69 ° C., IR (KBr) 3295 (≡C—H) 2130 (C≡C) 1720 (C═O) cm ⁻¹ , ¹ H-NMR (200 MHz) δ2.55 (brt, 1H, HC ≡C), 5.02 (m, 2H, HC≡CCH ₂ OCO), 7.47-7.67 (m, 3H, aromatic), 7.89 (d, 1H, aromatic), 8.05 (d 1H, aromatic), 8.26 (d, 1H, aromatic), 8.95 (d, 1H, aromatic)

(Synthesis Example 3)
Synthesis of 1-pyreneacetic acid 2-propynyl ester Propargyl alcohol 0.7 g (12.5 mmol), 1-pyreneacetic acid 2.0 g (7.7 mmol), p-toluenesulfonic acid monohydrate 0.1 g (0.5 mmol) ) Was reacted in 130 ml of chlorobenzene at 130 ° C. for 3 hours while distilling off the produced water. The product obtained by this reaction was purified by column chromatography to obtain 1.1 g (yield: 48%) of 1-pyreneacetic acid 2-propynyl ester.
Melting point: 102 to 103 ° C., IR (KBr) 3290 (≡C—H) 2130 (C≡C) 1740 (C═O) cm ⁻¹ , ¹ H-NMR (200 MHz) δ 2.47 (brt, 1H, HC ≡CCH ₂ OCO), 4.41 (s, 2H, HC≡CCH ₂ OCOCH ₂ -Pyrene), 4.72 (brd, 2H, HC≡CCH ₂ OCO), 7.94-8.28 (m, 9H , Aromatic)

(Synthesis Example 4)
Synthesis of 1-pyrenebutyric acid 2-propynyl ester Propargyl alcohol 2.0 g (35.7 mmol), 1-pyrenebutyric acid 5.0 g (17.3 mmol), p-toluenesulfonic acid monohydrate 0.5 g (2.6 mmol) ) Was reacted for 4 hours at 130 ° C. while distilling off the water produced in 100 ml of chlorobenzene. The product obtained by this reaction was purified by recrystallization (n-hexane / ethyl acetate = 5/1) to obtain 4.1 g (yield: 73%) of 1-pyrenebutyric acid 2-propynyl ester.
Melting point: 72-74 ° C., IR (KBr) 3260 (≡C—H) 2120 (C≡C) 1750 (C═O) cm ⁻¹ , ¹ H-NMR (200 MHz) δ 2.18-2.30 (m 2H, CH ₂ CH ₂ CH ₂ ), 2.48-2.56 (m, 4H, HC≡CCH ₂ OCO, CH ₂ CO), 3.38-3.45 (m, 2H, CH ₂ CH ₂ -Pyrene), 4.72 (brd, 2H , HC≡CCH 2 OCO), 7.85-8.34 (m, 9H, aromatic)

(Synthesis Example 5)
Synthesis of 2-propynyloxybenzene In the presence of 10.0 g (176.8 mmol) of propargyl alcohol in 900 ml of dimethyl sulfoxide (DMSO) in the presence of 40.0 g (356.8 mmol) of tert-butoxy potassium, 145.6 g (713. 6 mmol) at 90 ° C. overnight, and the resulting product was purified by distillation under reduced pressure to obtain 16.5 g (yield: 70%) of 2-propynyloxybenzene.
Boiling point: 66 to 67 ° C. (0.7 mmHg), IR (neat) 3290 (≡C—H) 2120 (C≡C) 1240 (O—C—O) cm ⁻¹ , ¹ H-NMR (200 MHz) δ2. 52 (brt, 1H, H C≡CCH 2 OPh), 4.70 (brd, 2H, HC≡CC H 2 OPh), 6.82-7.36 (m, 5H, HC≡CCH 2 O Ph)

(Synthesis Example 6)
Synthesis of 2-propynyl ester of butylcarbamic acid Add 5 ml of triethylamine to 5.66 g (100.9 mmol) of propargyl alcohol and 10.0 g (100.9 mmol) of butyl isocyanate, and react at 60 ° C. for 3 hours. Purification by distillation under reduced pressure yielded 13.63 g (yield: 87%) of butylcarbamic acid 2-propynyl ester.
Boiling point: 96 to 97 ° C. (0.7 mmHg), IR (neat) 3310 (≡C—H) 2130 (C≡C) 1720 (C═O) 1540 (C—N—H) 1250 (O—C—N) ) Cm ⁻¹ , ¹ H-NMR (200 MHz) δ 0.90 (t, 3H, C H ₃ CH ₂ CH ₂ CH ₂ —), 1.23-1.55 (m, 4H, CH ₃ C H ₂ C _{H 2 CH 2 -), 2.45} (t, 1H, H C≡CCH 2 O -), 3.18 (brq, 2H, CH 3 CH 2 CH 2 C H 2 NHCO -), 4.62 (brd 2H, HC≡CC H ₂ OCO-), 4.79 (brs, 1H, HC≡CCH ₂ OCON H Bu)

(Synthesis Example 7)
Synthesis of phenylcarbamic acid 2-propynyl ester To 4.71 g (83.9 mmol) of propargyl alcohol and 10.0 g (100.9 mmol) of phenyl isocyanate, 1 drop of pyridine was added at 0 ° C., and the mixture was reacted at 60 ° C. for 30 minutes. The obtained product was suspended and washed in hexane to obtain 13.41 g (yield: 91%) of phenylcarbamic acid 2-propynyl ester.
IR (KBr) 3290 (≡C—H) 2120 (C≡C) 1710 (C═O) 1550 (C—N—H) 1220 (O—C—N) cm ⁻¹ , ¹ H-NMR (200 MHz) δ2.53 (t, 1H, H C≡CCH 2 O -), 4.80 (brd, 2H, HC≡CC H 2 O -), 6.81 (brs, 1H, -OCON H Ph), 7. 07-7.43 (m, 5H, -OCONH Ph )

(Examples 1-7)
Using the propargyl alcohol derivative synthesized in Synthesis Examples 1 to 7 as a monomer, a polymerization reaction was performed on each.
That is, the propargyl alcohol derivative was taken in a reactor, and methanol (Examples 1, 2, 5 to 7) or tetrahydrofuran (Examples 3 and 4) was added so as to have the concentrations shown in Table 1. Next, after deaeration in the reactor, methanol suspensions (Examples 1, ₂ , 5 to 7) or tetrahydrofuran solutions (Examples 3 and 4) of [Rh (norbornadienyl) Cl] ₂ were used. In Examples 1-4 and 5-7, triethylamine (TEA) was further added as a co-catalyst. And it was made to react at 40 degreeC on the polymerization conditions of Table 1 for 4 hours. After completion of the polymerization reaction, the reaction product was once dispersed or reprecipitated in methanol, washed, filtered and dried. The stereoregularity of the obtained polymer was calculated from the NMR measurement with reference to the method described in the literature (C. I. Simionescu et al., Prog. Polym. Sci., 8 , 133-214, 1982). As a result, all the polymers were highly stereoregular with 70% or more.
The polymer was dissolved in chloroform, and the molecular weight was measured by GPC using the solution. The polymerization conditions and measurement results are shown in Table 1.

In addition, the polymer obtained in each example compares the chemical shift of the IR spectrum chart and NMR spectrum of the monomer and the polymer, the side chain substituent does not change, only the triple bond changes to a double bond. Therefore, it was confirmed to be a polymer. The IR spectrum chart of the polymer was confirmed mainly by the following IR spectrum assignment.
Example 1 (polyacetic acid 2-propynyl ester)
: IR (KBr) 1740 (C = O) cm ^-1
Example 2 (Poly 1-naphthalenecarboxylic acid 2-propynyl ester)
: IR (KBr) 1700 (C = O) cm ^-1
Example 3 (Poly 1-pyrene acetic acid 2-propynyl ester)
: IR (KBr) 1735 (C = O) cm ^-1
Example 4 (Poly 1-pyrenebutyric acid 2-propynyl ester)
: IR (KBr) 1735 (C = O) cm ^-1
: IR (KBr) 1240 (O—C—O) cm ⁻¹
Example 5 (poly-2-propynyloxybenzene)
: IR (KBr) 1240 (O—C—O) cm ⁻¹
Example 6 (polybutylcarbamic acid 2-propynyl ester)
: IR (KBr) 1700 (C═O) 1540 (C—N—H) 1250 (O—C—N) cm ⁻¹
Example 7 (polyphenylcarbamic acid 2-propynyl ester)
: IR (KBr) 1710 (C═O) 1540 (C—N—H) 1220 (O—C—N) cm ⁻¹
The IR spectrum chart and NMR spectrum of the polymer obtained in each Example are shown in FIGS.
In each of Examples 1 to 7, the polymer yield was as high as about 50% or more, and the Mw of the polymer was 6100 or more and the molecular weight was large.

(Comparative Example 1)
Polymerization of propargyl alcohol Polymerization was conducted in the same manner as in Example 1 except that propargyl alcohol was used instead of the propargyl alcohol derivative. After completion of the polymerization reaction, the reaction mixture was purified by a reprecipitation method using hexane, but no polymer was precipitated. Therefore, the entire reaction mixture was concentrated and dried under reduced pressure. When the molecular weight of the concentrate was measured by GPC, it was an oligomer and not a high molecular weight. The polymerization conditions and measurement results are shown in Table 1.

  The acetylene polymer obtained in the present invention includes battery materials such as lithium ion batteries and solar cells, resist materials, conductive materials such as organic semiconductors, pharmaceutical materials such as DDS and optical resolution agents, liquid crystal materials, organic EL, and organic LEDs. Can be applied to display materials such as non-linear materials, photoresponsive polymer materials, organic magnetic materials, polymer reaction reagents, line-type dosimeter materials, dielectric materials, contact lens materials, etc., especially useful for organic semiconductor materials and pharmaceutical-related materials It is.

2 is a diagram showing an IR spectrum of the polymer obtained in Example 1. FIG. 1 is a diagram showing an NMR spectrum of a polymer obtained in Example 1. FIG. 2 is a graph showing an IR spectrum of the polymer obtained in Example 2. FIG. 2 is a diagram showing an NMR spectrum of the polymer obtained in Example 2. FIG. 4 is a graph showing an IR spectrum of the polymer obtained in Example 3. FIG. 4 is a diagram showing an NMR spectrum of the polymer obtained in Example 3. FIG. 6 is a graph showing an IR spectrum of the polymer obtained in Example 4. FIG. 4 is a diagram showing an NMR spectrum of the polymer obtained in Example 4. FIG. 6 is a graph showing an IR spectrum of the polymer obtained in Example 5. FIG. 6 is a diagram showing an NMR spectrum of the polymer obtained in Example 5. FIG. 6 is a diagram showing an IR spectrum of the polymer obtained in Example 6. FIG. 6 is a diagram showing an NMR spectrum of the polymer obtained in Example 6. FIG. 6 is a diagram showing an IR spectrum of the polymer obtained in Example 7. FIG. 6 is a diagram showing an NMR spectrum of the polymer obtained in Example 7. FIG.

Claims (7)

  A method for producing an acetylene polymer, which comprises polymerizing a propargyl alcohol derivative in the presence of an organometallic complex. The method for producing an acetylene polymer according to claim 1, wherein the organometallic complex is a compound represented by the following general formula (I).
[ML _m L ′ _n ] _p X _q (I)
(Wherein, M is a group 7-10 element, L is a ligand derived from a compound having multiple bonds, L ′ is a ligand derived from a compound having a lone pair, X is an anion, m is (An integer of 0-7, n is an integer of 0-6, p is an integer of 1-2, q represents an integer of 0-2.) The method for producing an acetylene polymer according to claim 1 or 2, wherein the propargyl alcohol derivative is an ester compound represented by the following general formula (II).
CH≡C—CH ₂ —OCO—X ¹ (II)
(In the formula, X ¹ represents a hydrogen atom or an organic group.) The method for producing an acetylene polymer according to claim 1 or 2, wherein the propargyl alcohol derivative is an ether compound represented by the following general formula (III).
CH≡C—CH ₂ —O—X ² (III)
(In the formula, X ² represents an organic group.) The method for producing an acetylene polymer according to claim 1 or 2, wherein the propargyl alcohol derivative is a urethane compound represented by the following general formula (IV).
CH≡C—CH ₂ —OCONH-X ³ (IV)
(In the formula, X ³ represents an organic group.)   The acetylene-type polymer obtained by the manufacturing method of any one of Claims 1-5.   The acetylene polymer according to claim 6, wherein the mass average molecular weight (Mw) is 5600 or more and the dispersity (Mw / Mn) is 1 to 30.

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