WO2006004161A1

WO2006004161A1 - Novel polyphenylacetylene derivatives

Info

Publication number: WO2006004161A1
Application number: PCT/JP2005/012508
Authority: WO
Inventors: Toshio Masuda; Masashi Shiotsuki; Toshiki Kono; Yuichi Shida; Saeed Irfan
Original assignee: Kyoto University
Priority date: 2004-07-06
Filing date: 2005-07-06
Publication date: 2006-01-12
Also published as: JPWO2006004161A1

Abstract

Polyphenylacetylene derivatives in which each phenyl group has a hydroxy, amino, diester, dicarboxylic acid, or imido group. The polyphenylacetylene derivatives have a structure represented by the following formula (I), (II), or (III). (In the formulae, R1 is hydrogen or alkyl; R2 is alkyl; R3 is hydroxy or amino; and n is an integer of 10 or larger.)

Description

Specification

Novel polyphenylacetylene derivatives

Technical field

TECHNICAL FIELD [0001] The present invention relates to a novel polyacetylene derivative, and more particularly to a polyacetylene derivative having a hydroxyl group, an amino group, two esters, two carboxylic acids or imides on a phenyl group. .

Background art

[0002] Substituted acetylene can be polymerized with a suitable transition metal catalyst to give a high molecular weight polymer. The resulting polymer has a conjugated double bond in the main chain, and various properties such as deep coloration, photoconductivity, nonlinear optical properties, and material permeability based on conjugation of the main chain are normal bull polymers. Can not be expected.

[0003] Since substituted polyacetylene is a conjugated polymer having alternating double bonds in the main chain, the properties based on the conjugation of the main chain greatly depend not only on the substituents on the side chain but also on the degree of conjugation of the main chain. The polymer having the widest conjugation is polyacetylene having no substituent, and exhibits high conductivity equivalent to that of metal by appropriate doping. However, polyacetylene is insoluble and infusible, has poor moldability and is unstable in air, making it very difficult to apply as a functional material.

[0004] On the other hand, substituted polyacetylene having an appropriate substituent exhibits high solubility and stability, and provides a strong self-supporting film. Therefore, the potential application as a functional material is very large.

On the other hand, membrane separation is a resource-saving and energy-saving eco-friendly eco-technology and is expected to be used in many fields. Membrane separation, mainly used for water purification such as MF, UF, and RO, has advanced considerably in technology, and seawater desalination is actually widely used. On the other hand, gas separation and pervaporation separation are currently put to practical use only in limited fields. Therefore, it is necessary to develop a high-performance separation membrane that satisfies these conditions.

[0006] Substituted polyacetylene is characterized by having high material permeability, and the above-mentioned high performance It may be used for separation membranes.

[0007] Polyacetylene having a polar group as its substituent is expected to exhibit interesting permeation selectivity, but it is difficult to synthesize due to problems such as polymerization catalyst activity and high molecular weight. There are very few examples of these reports.

[0008] Examples of polyacetylene having a polar group include polyacetylene monoester having an ester at the para position of phenylacetylene (see Non-Patent Documents 1 to 4), and polyphenyl having an amide at the para position of phenylacetylene. -Ruacetylene monoamide (see Non-Patent Documents 5 and 6) has been reported.

[0009] In addition, the following reports have been reported on the polymerization of polyphenylacetylene derivatives having amino groups.

[0010] Tabata et al. First reported the polymerization of 4- (N, N-dimethylamino) phenylacetylene using a rhodium catalyst (see Non-Patent Document 7). However, it was difficult to obtain a high molecular weight polymer in a high yield, and most of the obtained polymers were oligomers.

[0011] In addition, Yashima et al. Reported the polymerization of 3-ethulurin and 4-etulurin using a rhodium catalyst (see Non-Patent Document 8). However, it was difficult to polymerize these monomers with a high yield, and the formed polymer was insoluble in ordinary organic solvents.

[0012] To date, no successful example has been reported for the polymerization of a polyacetylene derivative having a hydroxyl group.

[0013] [Non-Patent Document 1] Y. Kishimoto, M. Ito, T. Miyatake, T. Ikariya, and R. Noyori, Macromolecules, 28, 6662 (1995)

[Non-Patent Document 2] B. Z. Tang, X. Kong, X. Wan, and X. D. Feng, Macromolecules, 3

0, 5620 (1998)

[Non-Patent Document 3] X. Kong, J. W. Y. Lam, and B. Z. Tang, Macromolecules, 32, 172 2 (1999)

[Non-Patent Document 4] T. Aoki, M. Kokai, K. Shinohara, and E. Oikawa, Chem. Lett., 20 09 (1993)

[Special Article 5] E. Yashima, S. Huang, and Y. Okamoto, J. Am. Chem. Soc, Shi hem Commun "1811 (1994)

[Non-Patent Document 6] E. Yashima, S. Hung, T. Matsushima, and Y. Okamoto, Macromole cules, 28, 4184 (1995)

[Non-Patent Document 7] Tabata, M., Lindgren, M., Lee, H., Yokota, K., Yang, W. Polymer, 32 (8), 1531-1534, 1991.

[Non-Patent Document 8] Yashima, E., Maeda, Y., Matsushima, T., Okamoto, Y. Chirality, 9, 593-600, 1997.

As mentioned above, polyacetylene derivatives having monoesters or monoamides on the phenyl group have already been reported. Polyethylene derivatives having diesters, dicarboxylic acids or imides on the phenyl group have been reported in the past. Reported to,,,. In addition, polyacetylene derivatives having a hydroxyl group have been reported in the past.

[0014] On the other hand, a polyacetylene derivative having an amino group has been reported, but a polymer obtained by polymerization of 4- (N, N-dimethylamino) phenylacetylene described in Non-Patent Document 7 is This is different from the polyacetylene derivative of the present invention. In addition, since the polymer described in Non-Patent Document 8 is insoluble in the obtained polymer, the identification of the polymer, the measurement of the molecular weight, etc. have not been carried out, and whether or not the polymer is the same as the polyphenylacetylene derivative of the present invention. Is unknown.

[0015] The present invention has been made in view of the above-mentioned problems, and the object thereof is a hydroxyl group, an amino group, two esters, and two carbos on a phenol group that has not been reported or confirmed so far. The object is to provide a polyphenylacetylene derivative having an acid or an imide.

Disclosure of the invention

In order to solve the above-mentioned problems, the present inventors synthesized a phenylacetylene compound having a diester, dicarboxylic acid or imide on a phenol group, and superposed these monomers. Polyphenylacetylene derivatives having diesters, dicarboxylic acids or imides were successfully synthesized. Furthermore, the present inventors polymerized a phenylacetylene monomer having a structure in which a hydroxyl group or an amino group is protected by a substituent, and deprotected the resulting polymer to obtain a polyphenol having a hydroxyl group or an amino group. Ruacetylene induction The body was successfully synthesized and the present invention was completed.

That is, the polyacetylacetylene derivative according to the present invention is characterized by having a structure represented by the following general formula (I), (Π) or (ΠΙ)! /

[0018] [Chemical 1]

(Wherein R ¹ is hydrogen or an alkyl group, R ² is an alkyl group, R ³ is a hydroxyl group or an amino group, and n is an integer of 10 or more.)

R ¹ in the above formula (I) is preferably a linear alkyl group having 10 or less carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group or an n-hexyl group.

In the above formula (Π), R ² is preferably a linear alkyl group having 15 or less carbon atoms, more preferably an n-dodecyl group.

In the above formula (III), R ³ is preferably in the para position or the meta position.

[0021] Further, the polyacetylene derivative according to the present invention is characterized by having a structure represented by the following general formula (IV).

[0022] [Chemical 2]

(Where R ⁴ is

[0023] [Chemical 3]

Or

[0024] [Chemical 4]

And n is an integer of 10 or more. )

R ⁴ is preferably in the para position or the meta position.

[0025] The polyphenylacetylene derivative according to the present invention preferably has a weight average molecular weight of 10,000 or more.

[0026] With the above configuration, a new and highly polar polyphew that has not been reported or confirmed in the past.

-A ruacetylene derivative can be realized.

[0027] The conductive resin composition according to the present invention contains the polyacetylene derivative according to the present invention, and further includes a compound serving as an electron donor or acceptor as a dopant. It is characterized by that.

[0028] With the above configuration, a highly conductive rosin composition can be realized.

[0029] The phenylacetylene compound according to the present invention is such that one hydrogen atom of acetylene is benzene. A phenylacetylene compound substituted with a substituent containing a ring, and having a structure represented by the following formula (V) or (VI)! /

[Chemical 5]

[0031] [6]

Each of the above-mentioned phenylacetylene compounds is a novel substance that has not been reported so far, and the above-mentioned polyacetylene derivative according to the present invention can be obtained by polymerizing these compounds as raw materials.

[0032] The method for producing a polyphenylacetylene derivative according to the present invention comprises deprotecting a polyphenylacetylene derivative having a structure in which a hydroxyl group or an amino group bonded to a phenyl group is protected with a substituent, and the following general formula: (III)

[0033] [Chemical 7]

(Wherein R ³ is a hydroxyl group or an amino group, and n is an integer of 10 or more.) Characterized in that it comprises a step of producing a polyacetylene derivative represented by:

[0034] The method for producing a polyacetylene derivative according to the present invention includes the following general formula (IV):

[0035] [Chemical 8]

(Where R ⁴ is

[0036] [Chemical 9]

Or

[0037] [Chemical 10]

And n is an integer of 10 or more. )

By deprotecting the polyacetylene derivative having the structure represented by the following general formula (III)

[0038] [Chemical 11]

(Wherein R ³ is a hydroxyl group or an amino group, and n is an integer of 10 or more.)

It may include a step of producing a polyacetylene derivative represented by

[0039] Further, the method for producing a polyacetylene derivative according to the present invention preferably includes a step of producing a polyacetylacetylene derivative having a structure represented by the above general formula (IV). Preferably, the method includes a step of forming a film of a polyacetylacetylene derivative having a structure represented by (IV).

[0040] In the process for producing a polyacetylacetylene derivative according to the present invention, a rhodium catalyst may be used when producing a polyacetylacetylene derivative having a structure represented by the general formula (II). In particular, using [Rh (nbd) Cl] as the main catalyst and K as the cocatalyst

2

N (SiMe) is preferably used.

3 2

[0041] The production method described above makes it possible to produce the high molecular weight polyacetylene derivative according to the present invention in a high yield.

[0042] Still other objects, features, and advantages of the present invention will be sufficiently enhanced by the following description. The benefits of the present invention will also become apparent in the following description.

BEST MODE FOR CARRYING OUT THE INVENTION

An embodiment of the present invention will be described as follows. The present invention is not limited to this.

[Polyacetylene derivative having two esters, two carboxylic acids or imides on the phenyl group]

The polyphenylacetylene derivative according to the present invention has a structure represented by the above formula (I), and R ¹ may be hydrogen or an alkyl group. R ¹ alkyl group is especially Although not limited, a linear alkyl group having 10 or less carbon atoms is preferable. More preferably, it is a linear alkyl group having 1 to 6 carbon atoms. A linear alkyl group having 10 or less carbon atoms imparts sufficient solubility to the polymer, and its raw materials are readily available. Examples of the linear alkyl group having 10 or less carbon atoms include a methyl group, an ethyl group, an n-butyl group, and an n-hexyl group.

[0045] In addition, the polyacetylene derivative according to the present invention has a structure represented by the above formula (R), and R ² may be an alkyl group. The alkyl group for R ² is not particularly limited, but a linear alkyl group having 15 or less carbon atoms is preferable. More preferably, it is a linear alkyl group having 1 to 12 carbon atoms. A linear alkyl group having 15 or less carbon atoms imparts sufficient solubility to the polymer, and its raw materials are readily available. Examples of the linear alkyl group having 15 or less carbon atoms include n-dodecyl group.

[0046] The polyphenylacetylene derivative according to the present invention may have a polymerization degree n of 10 or more.

Preferably, it is selected within the range of 100 to 10 ⁷ .

[0047] The molecular weight of the polyacetylene derivative according to the present invention is not particularly limited, but the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more. It is particularly preferred to be over 100,000. V, most preferably over 500,000. If the weight average molecular weight is less than 10,000, sufficient mechanical strength can be secured!

[0048] The polyacetylacetylene derivative having the structure represented by the above formula (I) or (II) can be produced, for example, as follows. That is, it can be produced by polymerizing a phenylacetylene compound (raw material monomer) which is a repeating unit in a dry inert gas atmosphere in an appropriate solvent in the presence of a catalyst. The concentration of the raw material monomer in the solution is 0.1 M to 2 M, preferably 0.5 M to 1 M. The reaction temperature is 0 ° C ~ 80. C, preferably in the range of 30 ° C to 60 ° C, and in the range of 60 minutes to 48 hours reaction time.

[0049] Examples of the inert gas include nitrogen and argon.

[0050] As the solvent, various solvents can be used depending on the type of the monomer and the catalyst. For example, hydrocarbon (aliphatic hydrocarbon, aromatic hydrocarbon, etc.), halogenated hydrocarbon, Alcohols, nitrogen compounds, ethers, ketones, fatty acids, esters and the like can be mentioned. Of these, tetrahydrofuran (THF), toluene, chloroform, etc., which dissolve the catalyst and the produced polymer well, are preferable. The solvent may be a mixed solvent in which two or more types are mixed.

[0051] As the catalyst, a transition metal catalyst is preferred. For example, [Rh ⁺ (nbd) (r? ⁶ -CH) B "Ph]

6 5 3

, [(Norbornadiene) RhCl] / amine type, and the like.

2

[0052] The phenylacetylene compound as the raw material monomer may have any structure represented by the following general formula (VII) or (VIII). Further, the compound is not limited to a novel compound, and may be a known compound.

[0053] [Chemical 12]

■ ■ ■ (VIII)

(Wherein R ¹ is hydrogen or an alkyl group, and R ² is an alkyl group.)

Examples of phenylacetylene compounds that can be used as raw material monomers include dimethyl 4-ethyl phthalate, dimethyl 4-ethyl phthalate, dipropyl 4-ethyl phthalate, diisopropyl 4-ethyl phthalate, dibutyl 4-ethyl phthalate, 4-ethyl phthalate diisobutyl, 4-ethyl phthalate di-S-butyl, 4-ethyl phthalate dipentyl, 4-ethyl phthalate dihexyl, N-octyl-4-ethyl phthalimide, N-nor- Examples include 4-ethyl-phthalimide, N-decyl-4-ethyl-phthalimide, N-undecyl-4-ethyl-phthalimide, and N-dodecyl-4-ethyl-phthalimide. These raw material monomers can be synthesized using, for example, commercially available 4-ethyl phthalic anhydride as a raw material (see Examples described later;).

The polyacetylacetylene derivative having the structure represented by the above formula (I) or formula (II) can be suitably used for a gas separation membrane or a liquid separation membrane. An example of the gas separation membrane is an oxygen-enriched membrane. Examples of liquid separation membranes include ethanol separation membranes synthesized using biomass. In addition, diester, diester Since it has a carboxylic acid or an imide, it can be expected to be used in a wider range than conventional substituted polyacetylene, which has a very high polarity.

[0055] Further, the polyacetylene derivative according to the present invention is a conductive resin compound containing the polyphenylacetylene derivative and further containing a compound serving as an electron donor or acceptor as a dopant. Can be used. The conductive resin compound is not limited as long as it contains at least the primer phenylacetylene derivative according to the present invention and the above-mentioned dopant, for example, other polymers such as V are included. Okay, that's ugly.

[0056] Examples of the dopant include proton acids such as HC1, HBr, HI, perchloric acid and sulfuric acid, halogens such as chlorine, bromine and iodine, antimony pentafluoride, phosphorus pentafluoride, arsenic pentafluoride, Examples thereof include Lewis acids such as boron fluoride and ferric chloride, and electron acceptors such as tetracyanethylene.

[Phenolacetylene compound having two esters or imides on the phenyl group] The phenylacetylene compound according to the present invention has a structure represented by the above formulas (V) and (VI). It is what you have. These phenylacetylene compounds shown in (V) and (VI) are novel compounds that have not been reported so far.

[0058] (V) is di-n-butyl 4-ethynylphthalate, which is polymerized to produce poly (4-n-butyl phthalate) (in formula (I) above, R ¹ is a polyacetylene derivative which is an n-butyl group). Further, (VI) is N-dodecyl-4-ethynyl-phthalimide, and by polymerizing this, poly (N-dodecyl-4-ethur-phthalimide) according to the present invention (in the above formula (式), R ² Is a n-dodecyl group).

[0059] There are no particular limitations on the method for producing the phenylacetylene compound shown in (V) and (VI) above. The di-n-butyl 4-ethyl phthalate of (V) above can be produced, for example, by mixing commercially available 4-ethyl phthalic anhydride and n-butanol, adding sulfuric acid and stirring with heating. .

[0060] In addition, N-dodecyl-4-ethyl-phthalimide of (VI) above is prepared by, for example, dissolving commercially available 4-ethyl phthalic anhydride and n-dodecylamine in toluene, and using a Dean-Stark trap. It can be produced by heating to reflux.

The following will describe another embodiment of the present invention. The present invention is not limited to this! /.

[Polyphenylacetylene derivative having a hydroxyl group or an amino group]

The polyphenylacetylene derivative according to the present invention has a structure represented by the above formula (III), and R ³ may be a hydroxyl group or an amino group. R ³ is preferably in the para or meta position. Specifically, the following formula (IX) is a polyacetylacetylene derivative having a hydroxyl group at the para position, the following formula (X) is a polyphenylacetylene derivative having a hydroxyl group at the meta position, and the following formula (XI) is a para position A polyphenylene acetylene derivative having an amino group in the formula, and the following formula (XII) is a polyphenylene acetylene derivative having an amino group at the meta position.

[0063] [Chemical 13]

The polyacetylene derivative according to the present invention has a structure represented by the above formula (IV), and R ⁴ is

(Hereafter referred to as “OSiMe t-Bu”.)

Or

[0065] [Chemical 15]

(Hereafter referred to as “NHCO t-Bu”.)

2

If it is. R ⁴ is preferably in the para or meta position. Specifically, the following formula (ΧΠΙ) is a polyacetylene derivative having OSiMe t-Bu in the para position,

2

The following formula (XIV) is a polyacetylene derivative having OSiMe-t-Bu in the force meta position.

2

The following formula (XV) is a polyacetylene derivative having NHCO t-Bu in the para position

2

And is a polyacetylene derivative having NHCO t-Bu at the position of the following formula (XVI).

[0066] [Chemical 16]

(XV) The polyphenylacetylene derivative according to the present invention may have a polymerization degree n of 10 or more. Preferably, it is selected within the range of 100 to 10 ⁷ .

[0067] The molecular weight of the polyacetylene derivative according to the present invention is not particularly limited, but the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more. It is particularly preferred to be over 100,000. V, most preferably over 500,000. If the weight average molecular weight is less than 10,000, sufficient mechanical strength can be secured!

[0068] Polyphenylacetylene derivatives having the structure represented by the above formula (III) can be suitably used for high-performance separation membranes such as gas separation membranes and liquid separation membranes. An example of the gas separation membrane is an oxygen-enriched membrane. The oxygen-enriched film can be applied to, for example, an air conditioner having an oxygen-enriching function. Examples of liquid separation membranes include ethanol separation membranes synthesized using biomass. [Method for Producing Polyphenylacetylene Derivative Having Hydroxyl Group or Amino Group] The method for producing polyphenylacetylene according to the present invention comprises a polyphenyl having a structure in which a hydroxyl group or amino group bonded to a phenyl group is protected by a substituent. Any method may be used as long as it includes a step of producing the polyacetylacetylene derivative represented by the above general formula (III) by deprotecting the acetylene derivative.

[0070] The substituent for protecting the hydroxyl group or amino group (hereinafter, also referred to as "protecting group") is not particularly limited. However, the substituent is bulky and sufficiently protects the polar group. Don't react! Substituents with / ヽ and ヽぅ characteristics are preferred ヽ. Specific examples include t-butyldimethylsilyl group, t-butoxycarbonyl group, and trityl group.

Accordingly, the polyacetylene derivative having a structure in which the hydroxyl group or amino group bonded to the phenyl group is protected with a substituent is not particularly limited, and the polyacetylene derivative derivative having the protecting group shown in the above example is not particularly limited. If so! More specifically, a polyacetylene derivative having a structure represented by the above formulas (XIII) to (XVI) can be mentioned.

[0072] The method for deprotecting the substituent protecting the hydroxyl group or amino group is not particularly limited, and a known method may be appropriately selected and used. For example, when a t-butyldimethylsilyl group is used as a protecting group (for example, the above formulas (XIII) and (XIV)) or when a t-butoxycarbonyl group is used (for example, the above formulas (XV) and (XVI) ) Can be deprotected by immersing in a mixed solution of trifluoroacetic acid and water or an organic solvent such as hexane.

[0073] In addition, in the method for producing a polyacetylene derivative according to the present invention, a polyacetylene derivative having a structure represented by the above general formula (IV) (for example, the above formula (XIII) to It is preferable to include a step of producing a polyacetylene derivative having a structure represented by (XVI).

[0074] The polyacetylene derivative having the structure represented by the general formula (IV) is obtained by polymerizing a phenylacetylene compound (monomer) having the structure represented by the following general formula (XVII). It can be manufactured from Tsujiko.

[0075] [Chemical 17]

(X V I I)

(Where R ⁵ is OSiMe t— Bu or NHCO t— Bu)

twenty two

Here, the production method of the monomer represented by the general formula (XVII) is not particularly limited, and a known method may be appropriately selected and produced. For example, it can be produced by the method described in Examples described later.

[0076] The method for polymerizing the monomer is not particularly limited, and may be produced by appropriately selecting a known polymerization method. For example, it can be produced as follows.

That is, it can be produced by polymerizing the monomer in a suitable solvent in the presence of a catalyst in a dry inert gas atmosphere. The concentration of the monomer in the solution is adjusted to be in the range of 0.1 ~ 2 ~, preferably 0.5M ~ l ~. The reaction temperature is selected in the range of 0 ° C to 80 ° C, preferably 30 ° C to 60 ° C, and the reaction time is selected in the range of 60 minutes to 48 hours.

[0078] Examples of the inert gas include nitrogen and argon.

[0079] Various solvents can be used as the solvent depending on the kind of the monomer and the catalyst. For example, hydrocarbons (aliphatic hydrocarbons, aromatic hydrocarbons, etc.), halogenated hydrocarbons, alcohols, nitrogen compounds, ethers. , Ketones, fatty acids, esters and the like. Of these, tetrahydrofuran (THF), toluene, chloroform, etc., which dissolve the catalyst and the produced polymer well, are preferable. The solvent may be a mixed solvent in which two or more types are mixed.

[0080] As the catalyst, a rhodium catalyst is particularly preferable among transition metal catalysts.

Examples of rhodium catalysts include [Rh (nbd) Cl], Rh ⁺ (nbd) [h ⁶ -CHB "(CH)] and the like.

2 6 5 6 5 3

However, the present invention is not limited to this. In this production method, it is most preferable to use [Rh (nbd) Cl] as the main catalyst and KN (SiMe) as the cocatalyst.

2 3 2

[0081] Further, in the method for producing a polyacetylene derivative according to the present invention, a polyacetylene derivative having a structure represented by the above general formula (IV) (for example, the above formula Preferably, the method includes a step of forming a film of a polyacetylene derivative having a structure represented by (XIII) to (XVI). By deprotecting the protecting group after film formation, there is an advantage that a polymer film that cannot be synthesized conventionally or a polymer film that is insoluble in an organic solvent can be produced.

[0082] The method of film formation is not particularly limited, and a known method may be appropriately selected and used. For example, a casting method using a polymer solution can be suitably used.

[0083] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[0084] Examples 1. Polyacetylene derivatives having two esters, two carboxylic acids or imides on the phenolic group>

1. Synthesis of monomers (phenylacetylene compounds)

〔material〕

Commercially available 4-ethyl phthalic anhydride (following formula (XVIII), manufactured by Fuji Photo Film Co., Ltd., trade name KK-1) was used as a raw material for monomer synthesis.

[0085] [Chemical 18]

(Synthesis of dimethyl 4-ethynylphthalate (Compound 2))

In a 200 mL eggplant flask, add 4.0 g (23 mmol) of 4-ethyl phthalic anhydride (compound 1) and 186 mL (4.6 mol) of methanol, add 2.0 mL of H 2 SO 2 with stirring, and heat. 24 ° C

twenty four

The mixture was stirred with heating for a period of time (see the following scheme (1)). After completion of the reaction, the solvent was distilled off under reduced pressure and extracted with ethyl acetate. The organic layer was washed with an aqueous sodium hydrogen carbonate solution and water, and dehydrated by adding anhydrous sodium sulfate to the organic layer solvent. Anhydrous sodium sulfate was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain 4.1 g of a crude product as a yellow solid. The resulting crude product was purified by flash column chromatography (stationary phase—silica gel, moving bed—ethyl acetate) -Dimethyl phthalate (yellow solid) was obtained (yield 3.3 g, yield 65%).

[0086] [Chemical 19]

1 ¹ H-NMR spectrum and ¹³ C-NMR spectrum of compound 2 (dimethyl 4-ethyl phthalate) are shown below.

^J H NMR (DMSO-d): 7.86 (m, 3H, Ar), 4.62 (s, 1H, sp-CH), 3.93 (s, 6H, OCH).

6 3

¹³ CfH} NMR (DMSO-d): 166.46 (C = 0), 134.40 (Ar), 132.10 (Ar), 131.49 (Ar), 130.

6

89 (Ar), 129.24 (Ar), 125.01 (Ar), 84.21 (sp- CH), 81.49 (sp— C), 52.78 (OCH), 52.7

Three

5 (OCH).

Three

[Synthesis of 4-ethyl ethynyl phthalate (Compound 2)]

Into a 500 mL eggplant flask, add 3.0 g (17 mmol) of 4-ethyl phthalic anhydride (Compound 1) and 203 mL (3.5 mol) of ethanol, add 1.1 mL of H 2 SO 2 with stirring, and heat. 24 ° C

twenty four

The mixture was stirred with heating for a period of time (see the following scheme (2)). After completion of the reaction, the solvent was distilled off under reduced pressure and extracted with ethyl acetate. The organic layer was washed with an aqueous sodium hydrogen carbonate solution and water, and dehydrated by adding anhydrous sodium sulfate to the solvent of the organic layer. Anhydrous sodium sulfate was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a crude product as a yellow liquid. The resulting crude product was purified by flash column chromatography (stationary phase—silica gel, moving bed—ethyl acetate / hexane 1/3 v / v) to obtain compound 3, 4-ethyl phthalate (yellow liquid). Obtained (yield 2.3 g, 53% yield).

[0087] [Chemical 20]

¹ H—NMR ^ vector and ¹³ C—NM of compound 3 (jetyl 4-ethyl phthalate) The R spectrum is shown below.

1H NMR (DMSO-d): 7.72 (m, 3H, Ar), 4.47 (s, 1H, sp-CH), 4.26 (q, 4H, OCH), 1

6 2

.26 (t, 6H, CH).

Three

¹³ CfH} NMR (DMSO-d): 165.99 (C = 0), 165.94 (C = 0), 134.21 (Ar), 132.32 (Ar), 1

6

31.44 (Ar), 131.22 (Ar), 129.14 (Ar), 124.86 (Ar), 83.97 (sp-CH), 81.48 (sp— C), 61. 54 (OCH), 61.49 (OCH), 13.76 (CH) , 13.74 (CH).

2 2 3 3

[Synthesis of 4-n-butyl 4-ethynylphthalate (Compound 4)]

In a 1 L eggplant flask, add 4.0 g (23 mmol) of 4-ethyl phthalic anhydride (compound 1) and 425 mL (4.6 mol) of n-butanol, add 1.8 mL of H 2 SO 2 with stirring, and heat. 24 hours at 50 ° C

twenty four

The mixture was stirred with heating (see the following scheme (3)). After completion of the reaction, the solvent was distilled off under reduced pressure and extracted with ethyl acetate. The organic layer was washed with an aqueous sodium hydrogen carbonate solution and water, and dehydrated by adding anhydrous sodium sulfate to the solvent of the organic layer. Anhydrous sodium sulfate was removed by filtration, and the filtrate was distilled off under reduced pressure to obtain a crude product as a yellow liquid. The resulting crude product was purified by flash column chromatography (stationary phase—silica gel, moving bed—ethyl acetate / hexane 1/9 v / v) to give compound 4 di-n-butyl 4-ethylphthalate (yellow (Liquid) was obtained (yield 3.1 g, yield 45%).

[Chemical 21]

The ¹ H—NMR ^ vector and ¹³ C—N MR spectrum of Compound 4 (di-n-butyl 4-ethyl phthalate) are shown below.

^J H NMR (DMSO-d): 7.72 (m, 3H, Ar), 4.48 (s, 1H, sp-CH), 4.20 (vq, 4H, OCH),

6 2

1.61 (vt, 4H, CH) 1.34 (m, 4H, CH) 0.88 (t, 6H, CH).

2 2 3

¹³ CfH} NMR (DMSO-d): 166.01 (C = 0), 165.98 (C = 0), 134.23 (Ar), 132.34 (Ar), 1

6

31.40 (Ar), 131.22 (Ar), 129.15 (Ar), 124.88 (Ar), 84.01 (sp-CH), 81.45 (sp— C), 65. 22 (OCH), 65.16 (OCH), 29.95 (CH) , 29.92 (CH), 18.62 (CH), 13.45 (CH). [Synthesis of 4-n-hexyl 4-ethynylphthalate (Compound 5)]

Into a 200 mL eggplant flask, add 0.93 g (5.4 mmol) of 4-ethyl phthalic anhydride (Compound 1), 101 mL (809 mmol) of n-hexanol, add 0.5 mL of H 2 SO 4 with stirring, and heat. 50

twenty four

The mixture was heated and stirred at ° C for 20 hours (see the following scheme (4)). After completion of the reaction, the solvent was distilled off under reduced pressure and extracted with ethyl acetate. The mixture was washed with an aqueous sodium hydrogen carbonate solution and water, and anhydrous sodium sulfate was added to the solvent of the organic layer and left for half a day for dehydration. Anhydrous sodium sulfate was removed by filtration, and the solvent of the organic layer was distilled off under reduced pressure to obtain a crude product as a yellow liquid. The resulting crude product was purified by flash column chromatography (stationary phase 1 silica gel, moving bed 1 ethyl acetate / hexane 1/1 v / v) to give compound 5 di-n-hexyl 4-ethylphthalate. (Yellow liquid) was obtained (yield 1.39 g, yield 72%).

[Chemical 22]

The ¹ H-NMR ^ vector and ¹³ C-NMR spectrum of compound 5 (di-n-hexyl 4-ethyl phthalate) are shown below.

^J H NMR (DMSO-d): 7.72 (m, 3H, Ar), 4.47 (s, 1H, sp-CH), 4.18 (t, 4H, OCH), 1.

6 2

61 (m, 4H, CH) 1.25 (m, 12H, CH), 0.83 (t, 6H, CH).

2 2 3

^ Ci'H} NMR (DMSO-d): 166.59 (C = 0), 166.53 (C = 0), 134.81 (Ar), 132.89 (Ar), 1

6

31.98 (Ar), 131.80 (Ar), 129.73 (Ar), 125.46 (Ar), 84.62 (sp-CH), 82.02 (sp— C), 66. 10 (OCH), 66.03 (OCH), 28.45 (CH) , 25.63 (CH), 22.55 (CH), 14.34 (CH).

2 2 2 2 2 3

[Synthesis of N-dodecyl-4-ethyl-phthalimide (Compound 6)]

Into a 50 mL eggplant flask, add 0.50 g (2.9 mmol) of 4-ethyl phthalic anhydride (compound 1), 0.53 g (2.9 mmol) of n-dodecylamine, add 30 mL of toluene as a solvent, and add Dean-Stark The trap was assembled and heated to reflux at 140 ° C for 12 hours (see scheme (5) below). After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product as a yellow solid. The obtained crude product is Purification by oral matography (stationary phase—silica gel, moving bed—ethyl acetate / hexane 1/3 v / v) gave N-dodecyl-4-ethyl-phthalimide (yellow solid) of compound 6 ( Yield 0.95 g, yield 97%).

[0090] [Chemical 23]

The ¹ H-NMR spectrum and ¹³ C NMR spectrum of compound 6 (N-dodecyl-4-ethyl-phthalimide) are shown below.

1H NMR (CDC1): 7.91 (s, 1H, Ar), 7.78 (s, 2H, Ar), 3.67 (vt, 2H, NCH), 3.32 (s, 1

3 2

H, sp-CH), 1.66 (m, 2H, CH), 1.24 (m, 18H, CH) 0.88 (t, 3H, CH).

2 2 3

¹³ CfH} NMR (CDC1): 167.64 (C = 0), 167.53 (C = 0), 137.36 (Ar), 132.30 (Ar), 131.5

Three

7 (Ar), 128.08 (Ar), 126.56 (Ar), 123.06 (Ar), 81.84 (sp-CH), 81.42 (sp— C), 38.28 (NCH), 31.92 (CH), 29.63 (CH), 29.57 (CH), 29.50 (CH), 29.36 (CH), 29.18 (C

2 2 2 2 2 2

H), 28.57 (CH), 26.87 (CH), 22.71 (CH), 14.15 (CH).

2 2 2 2 3

2.Polymerization

Each of the above monomers (phenylacetylene compound, compounds 1 to 5) was polymerized to obtain the following polyacetylene derivatives (pol _y (l) to ( ⁵ )).

[0091] [Chemical 24]

Table 1 shows the yield, weight average molecular weight (Mw), and weight average content of each polymer (poly (l) to poly (5)) obtained by polymerization of each monomer (phenylacetylene compound, compounds 1 to 5). The ratio of molecular weight to number average molecular weight (MwZMn) is shown. The molecular weight of the polymer was measured by GPC (PSt conversion).

[table 1]

As a typical example of the polymerization reaction, a polymerization method of poly (4-ethyl phthalate) (poly (l)) will be described.

Diethyl 4-ethyl phthalate 218.14 to 1 mL of distilled THF under dry nitrogen atmosphere mg (1 mmol) dissolved in distilled THF 1 mL [Rh + (nbd) (r? ⁶ -CH) B "Ph

6 5 3

] 2.0 mg (2.5 / z mol) of the catalyst was added to the dissolved mixture, and kept at 30 ° C for 1 hour in a thermostatic bath. The resulting polymer was purified by reprecipitation in a large amount of methanol. In a similar manner, poly (4-ethyl phthalate) (poly (2)), poly (4-ethyl phthalate) (poly (3)) and poly (4-ethyl phthalate) (Xyl) (poly (4)) can be obtained.

[0094] For poly (N-dodecyl-4-ethyl-phthalimide) (poly (5))! /, The polymerization time was 15 minutes, and the black mouth form soluble part (soluble part / insoluble part) 9/1) was purified by reprecipitation in a large amount of acetone.

[0095] Poly (4-Echurufutaru dimethyl) (poly (l)) was identified by IR, .eta. NMR and ¹³ C-NMR. The results are shown below.

IR (KBr, cm " ¹ ): 2940, 1730, 1436, 1295, 1130, 1069, 1069.

JH NMR (CDCL): 7.32, 7.14, 6.80, 5.70, 3.75, 3.73.

Three

^ Ci'H} NMR (CDCL): 167.64, 166.84, 144.26, 138.88, 132.49, 132.14, 129.90, 12

Three

9.20, 127.37, 52.57, 52.47.

Poly (4-ethyl phthalate) (poly (2))

More identified. The results are shown below.

^J H NMR (CDCL): 7.33, 7.19, 6.73, 5.68, 4.17, 1.22, 1.15.

Three

^ Ci'H} NMR (CDCL): 167.27, 166.38, 144.32, 138.96, 132.81, 132.01, 130.02, 12

Three

9.09, 127.61, 61.48, 61.34, 14.03, 13.93.

Poly (4-ethyl phthalate di n-butyl) (poly (3)) was identified by 1 H-NMR and ¹³ C-NMR. The results are shown below.

1H NMR (CDCL): 7.33, 7.19, 6.76, 5.69, 4.10, 1.58, 1.48, 1.33, 1.23, 0.88, 0.79.

Three

¹³ CfH} NMR (CDCL): 167.36, 166.29, 144.48, 144.42, 139.05, 132.97, 132.00, 12

Three

9.86, 129.18, 127.89, 65.29, 65.31, 30.51, 30.32, 19.08, 18.98, 13.70, 13.62.

Poly (4-n-hexylphthalate) (poly (4)) was identified by 1 H-NMR and ¹³ C-NMR. The results are shown below.

^J H NMR (CDCL): 7.36, 7.20, 6.81, 5.70, 4.13, 1.63, 1.53, 1.29, 1.21, 0.87. C {H} NMR (CDCL): 167.40, 166.21, 139.03, 132.99, 132.05, 129.73, 129.20, 12

Three

7.84, 65.58, 65.40, 31.51, 31.46, 28.49, 28.31, 25.54, 25.48, 22.56, 14.00.

Poly (N-dodecyl-4-ethyl-phthalimide) (poly (5)) was identified by ¹ H-NMR and ¹³ C-N MR. The results are shown below.

1H NMR (CDC1): 7.29, 7.06, 6.84, 5.76, 3.52, 1.58, 1.26, 0.88.

Three

¹³ CfH} NMR (CDC1): 167.01, 166.90, 139.12, 132.85, 132.61, 132.30, 131.44, 122

Three

.85, 120.91, 77.31, 31.95, 30.93, 29.75, 29.71, 29.40, 29.31, 28.53, 27.07, 22.71, 1 4.13.

3. Synthesis of poly (4-ethynylphthalic acid)

500 mg of poly (4-ethyl phthalate) having a weight average molecular weight of 660,000 was dissolved in 30 mL of THF, and ION NaOHaq was stirred for 30 hours at room temperature for 20 hours (see the following scheme (8)). The supernatant was removed, and the reddish brown precipitate was washed once with a small amount of distilled water and then dissolved in 25 mL of distilled water. This red homogeneous solution was added dropwise to 50 mL of IN HClaq to cause reprecipitation, and the solid obtained by filtration was dried under reduced pressure for 24 hours to obtain poly (4-ethylphthalic acid) (poly (6)) (reddish brown solid). Obtained (yield 481 mg, yield 96%). Poly (4-etulphthalic acid) (poly (6)) was identified by IR and ¹ H-NMR. The results are shown below.

IR (KBr, cm " ¹ ): 3500, 1720, 1560, 1540, 1295, 1143.

JH NMR (CD OD): 7.42, 7.03, 6.80, 5.90, 3.74.

Three

[Chemical 25]

po l y (6)

1.Synthesis of monomers

Monoma ~~ is a paper by Yashima et al. (Yashima, E.; Huang, S.; Matsusita, T.; Okamoto, Y Macromolecules 1995, 28, 4184.) In the above paper, only the method for synthesizing para-monomers is described.

[0097] The following scheme (9) shows the synthesis procedure and yield of the para isomer.

[0098] [Chemical 26]

-OH / PdCI ₂ (Ph ₃ P) ₂ / Ph ₃ P / Cul

Et ₃ N, 12h

-O— 一 ί-Bu colorless liquid

reflux, 8h

yield 94% yield 59%

Scheme (9) In addition, scheme (10) below shows the synthesis procedure and yield of the meta isomer.

[0099] [Chemical 27]

-OH / PdCI ₂ (Ph ₃ P) ₂ / Ph ₃ P / Cul

CISiMe ₂ i-Bu

Imidazole Et ₃ N, 12h

yield 94% colorless liquid

yield 88% yield 56% scheme (10)

2.Polymerization

The polymerization was performed using a rhodium (Rh) catalyst under a dry nitrogen atmosphere. Two types of rhodium catalysts were used: [Rh (nbd) Cl] and Rh + (nbd) [h ⁶ -CHB- (CH)]. Use [Rh (nbd) Cl]

2 6 5 6 5 3 2 was performed under the following conditions with Et N or KN (SiMe) as a cocatalyst.

3 3 2

. In distilled toluene, 30 ° C, 24 hours, [M] = 0.5 M, [Rh] = 5.0 mM or 10 mM o

, [Cocat] / [Cat] = 10. That is, a polymerization method in which a toluene solution of a monomer is mixed with a toluene solution of a catalyst and a cocatalyst. [0100] When Rh + (nbd) [h ⁶ -CHB "(CH)] is used as the main catalyst, the cocatalyst is not used.

6 5 6 5 3

The rhodium catalyst was used alone under the following conditions. In distilled toluene, 30 ° C, 24 hours, [M] = 0.5 M, [Cat] = 5.0 mM or 10 mM.

0

[0101] The polymerization solvent used was purified by distillation. The polymer was dropped into a large amount of methanol, and the methanol-insoluble part was recovered with a glass filter.

[0102] The results of the para-body are shown in Table 2. The main catalyst of run5 [Rh (nbd) Cl] and the cocatalyst KN (SiMe)

In the 2 3 2 combination, the molecular weight increased more than twice that of runl-4.

[0103] [Table 2] polymer '

run com plex add itive ⁰ yield M _w / 1 0 ^{4 e} M _w 1 M,

(%)

1 ^a [Rh (nbd) CI] ₂ Et ₃ N 65 88 8.0

2 ^b [Rh (nbd) CI] ₂ Et ₃ N 73 80 8.0

3 ^a Rh ⁺ (nbd) [^ ⁶ -C ₆ H ₆ B- (C ₆ H ₅ ) ₃ ]-53 48 6.2

4 ^b Rh ⁺ (nbd) [77 ⁶ -C ₆ H ₅ B— (C ₆ H ₅ ) ₃ ]-86 28 4.5

5 ^b [Rh (nbd) CI] ₂ KN (Si Me ₃ ) ₂ 61 21 0 10.0

a) In toluene, at 30, for 24 h; [M] ₀ = 0.5, [Rh] = 5.0 m M,

b) In toluene, at 30, for 24 h; [M] ₀ = 0.5 M, [Rh] = 10 mM. c) [Et ₃ N] / [Rh] = 10 d) Toluene-soluble and methano 卜 insoluble product e) Measured by GPC. The para-body was identified by ¹ H-NMR and IR. The results are shown below.

JH NMR (CDC1): 7.92, 6.83, 6.60, 0.95, 0.20.

Three

IR (KBr, cm " ¹ ): 2957, 1604, 1505, 1265, 1165, 912, 841, 783, 683.

Table 3 shows the results of the meta form. Similar to the result of the para-body, the molecular weight was greatly increased in the combination of the main catalyst [Rh (nbd) C1] of run5 and the cocatalyst KN (SiMe).

2 3 2

[Table 3] polymer ^d run complex additive ⁰ yield M _w / 10 ^{4 e} M _w 1 M _n ^e

(%)

1 ^a [Rh (nbd) CI] ₂ Et ₃ N 45 78 2.2

2 ^b [h (nbd) CI] ₂ Et ₃ N 60 130 4.5

3 ^a Rh ⁺ (nbd) [? 7 ⁶ -C ₆ H ₅ B- (C ₆ H ₅ ) 3]-55 52 6.0

4 ^b Rh ⁺ (nbd) [77 ⁶ -C ₆ H ₅ B- (C ₆ H ₅ ) ₃ ]-91 95 4.2

5 ^b [Rh (nbd) CI] ₂ KN (SiMe ₃ ) ₂ 69 570 8.0

a) In toluene, at 30, for 24 h; [M] ₀ = 0.5 M, [Rh] = 5.0 mM.

b) In toluene, at 30, for 24 h; [M] ₀ = 0.5, [Rh] = 10 mM. =) [Et ₃ N] / [Rh] = 10 d) Toluene-soluble and methano 卜 insoluble product, e) Measured by GPC. The meta form was identified by ¹ H-NMR and IR. The results are shown below.

'Η NMR (CDC1): 6.70, 6.37, 6.25, 5.64, 0.82, —0.06.

Three

IR (KBr, cm " ¹ ): 2957, 1595, 1570, 1494, 1482, 1258, 1148, 968, 783, 689.

3.Film formation

A free-standing membrane was prepared by casting a toluene solution of the polymer on a petri dish. The obtained meta polymer film (a polymer synthesized under the conditions of run 2 in Table 3) was a transparent and uniform film.

[0105] The gas permeability of the membrane was measured. The results are shown in Table 4. For all gases, the gas permeability of the diphenylacetylene membrane was lower. This is thought to be because the polymer film became quite dense due to one fewer phenyl group.

[0106] [Table 4]

Gas permeability coefTicients (P) of polymers

P (barrer)

He H ₂ 0 ₂ N ₂ C0 ₂ CH ₄

Polymer ⁰ 48 64 17 7.6 58 12 2.2

a) P values measured at 25 ° C.

b) 1 barrer = 1 x 10 " ¹⁰ cm ³ (STP) cm cm" ² s " ¹ cmHg ^-1 .

c) Methano 卜 conditioned. 4. Deprotection of polymer membrane (desilylation)

The desilylation reaction was performed by immersing the polymer film in a mixed solution of trifluoroacetic acid and water or an organic solvent for 24 hours.

[0107] Example 3. Polyacetylene Derivative Having Amino Group>

1.Synthesis of monomers

Monomers were synthesized by refluxing 3-ethulurin (meta) or 4-etulurin (para) and tert-butyl pyrocarbonate in tetrahydrofuran (THF).

[0108] The scheme and yield of monomer synthesis are shown in the following scheme (11).

[0109] [Chemical 28]

1a: mefa (yield = 89%)

Steam (11) 1b: para (yield = 82%)

Each monomer was identified by ¹ H-NMR and IR. The results of ¹ H-NMR and IR of the meta form are shown below.

^J H NMR (CDC1): 7.52, 7.35, 7.23, 7.16, 6.45, 3.04, 1.53.

Three

IR (KBr, cm '' ¹ ): 3340, 3310, 2952, 1698, 1605, 1530, 1479, 1454, 1367, 1242, 1154, 888, 870, 787, 685, 658.

The results of ¹ H-NMR and IR of the para form are shown below.

JH NMR (CDC1): 7.41, 7.32, 6.53, 3.02, 1.54.

Three

IR (KBr, cm '' ¹ ): 3390, 3295, 2957, 1705, 1609, 1584, 1559, 1512, 1408, 1316, 1231, 1156, 1056, 902, 837, 774, 761.

2.Polymerization The polymerization was carried out using a rhodium (Rh) catalyst in a Schlenk tube with a three-way stopcock under an argon atmosphere. 1.0 mL of THF solution containing 1.0 mmol of monomer, [Rh (nbd) Cl] 20.0 μ

2 mL of THF solution 1.0 mL and KN (SiMe) (15% solution, 10.0 mol)

3 2

27 μL of the solution was mixed and allowed to react at 30 ° C. for 24 hours with stirring.

[0110] When [Rh (nbd) Cl] is used as the main catalyst and Et N is used as the cocatalyst, Et N is added at a concentration of 100.0 μmol.

2 3 3

Polymerization was carried out in the same manner as described above except for use in 1. In addition, [Rh (nbd) BPh] (20

Four

When 0.0 mol) was used, the rhodium catalyst was used alone without using a cocatalyst.

[0111] The polymer was added dropwise to a large amount of hexane, and the hexane-insoluble portion was collected with a glass filter, washed with hexane, and dried under vacuum.

[0112] Table 5 shows the results of the meta form. Table 6 shows the results of the para body. A high molecular weight polymer was obtained in a high yield (80% to 95%) when any rhodium catalyst was used. Among them, in the combination of the main catalyst [Rh (nbd) Cl] of run5 in Table 5 and the cocatalyst KN (SiMe),

2 3 2

A very high molecular weight (310,000) polymer was obtained. Both the meta polymer and para polymer were yellow, soluble in organic solvents such as black mouth form, THF, acetone, and methanol, and immediately insoluble in hexane and toluene.

[0113] [Table 5]

Polymerization 01 Monomer (meta V

Polymer

Run Solvent Catalyst Co-Catalyst Yield

MM _D

(%)

1 Toluene ^ [Rh (nbd) Cl] ₂ Et ₃ N 88 131000 1 .8

2 [Rh (nbd) Cl], N (SiMe ₃ ) ₂ ^e 91 253000 1.9

_{3 Rh (nbd) BPh 4 -} 85 28000 2.4

4 THF [Rh (nbd) Cl] ₂ Et ₃ N, 83 131000 1 .8

5 [Rh (nbd) Cl] ₂ KN (SiMe ₃ ) ₂ ^e 89 310000 1 .7

_{6 Rh (nbd) BPh 4 -} 82 96000 2.2 a 30 ° C, 4 h; [M] 0 = 0.50 M, [Rh] two 2.0 mM.

^{b Hexane- insoluble product. c Measured by} GPC.

d Insoluble polymers were obtained in toluene but dissolved in THF. e [N] / [Rh] 1

f [N] / [Rh]-10

[0114] [Table 6]

Each polymer was identified by ¹ H-NMR and IR. The results of ¹ H-NMR and IR of the meta form are shown below.

^J H NMR (CDC1): 7.26, 6.70, 6.37, 5.71, 1.43.

Three

IR (KBr, cm '' ¹ ): 3324, 2952, 1685, 1635, 1559, 1507, 1457, 1362, 1234, 1154, 1056, 856, 785, 697.

The results of ¹ H-NMR and IR of the para form are shown below.

JH NMR (CDC1): 6.83, 6.57, 5.72, 1.48.

Three

IR (KBr, cm '' ¹ ): 3370, 2980, 1685, 1559, 1540, 1457, 1368, 1313, 1231, 1160, 1052, 836, 768.

3.Film formation

A free-standing membrane was prepared by casting a THF solution of the polymer synthesized under the conditions of run 5 in Table 5 onto a petri dish.

[0115] 4. Deprotection of polymer membrane

Deprotection was performed by immersing the polymer membrane in a mixed solution of trifluoroacetic acid and an organic solvent such as hexane for 24 hours.

[0116] It should be noted that the specific embodiments or examples made in the section of the best mode for carrying out the invention are merely to clarify the technical contents of the present invention. The present invention is not limited to specific examples and should not be construed in a narrow sense, and can be implemented with various modifications within the scope of the claims described below. Industrial applicability [0117] The polyacetylacetylene derivative according to the present invention has a hydroxyl group, an amino group, a diester, a dicarboxylic acid, or an imide in its repeating unit, and is therefore a very high molecular weight molecule. Therefore, if a membrane is formed using the polyacetylene derivative, a high-performance separation membrane having an unprecedented function can be realized, and the usable range is wide.

The polyacetylacetylene derivative according to the present invention can be used as a gas separation membrane such as an oxygen-enriched membrane or a liquid separation membrane such as a water purification membrane. The oxygen-enriched film can be applied to air conditioners with an oxygen-enriching function. Application to batteries is also expected.

Claims

The scope of the claims

The following general formula (I), (II) or (in)

One… (I I)

A polyphenylacetylene derivative having a structure represented by:

[2] The polyphenylacetylene derivative according to claim 1, wherein R ¹ in the formula (I) is a linear alkyl group having 10 or less carbon atoms.

[3] The polyphenylene acetylene derivative according to claim 2, which is a linear alkyl group having 10 or less carbon atoms, which is a methyl group, an ethyl group, an n-butyl group or an n-hexyl group. .

[4] The polyphenylacetylene derivative according to claim 1, wherein R ² in the above formula (Π) is a linear alkyl group having 15 or less carbon atoms.

[5] The polyacetylene derivative according to claim 4, wherein the linear alkyl group having 15 or less carbon atoms is an n-dodecyl group.

Le acetylene derivative - [6] Porifue according to claim 1, wherein the R ³ in formula (III) is characterized in that the para position or meta position. The following general formula (IV)

(Where R ⁴ is

[Chemical 3]

Or

[Chemical 4]

And n is an integer of 10 or more. )

A polyphenylacetylene derivative having a structure represented by:

[8] The polyphephine according to claim 3, wherein R ⁴ is in a para position or a meta position.

-Ruacetylene derivatives.

[9] The polyphenylacetylene derivative according to [1], wherein the weight average molecular weight is 10,000 or more, and the shear force is 1 according to claim 1.

[10] It is characterized in that it contains the polyacetylene derivative according to any one of claims 1 to 8 and further contains a compound serving as an electron donor or acceptor as a dopant. Conductive resin composition. A phenylacetylene compound in which one hydrogen atom of acetylene is substituted with a substituent containing a benzene ring,

The following formula (V) or (VI)

[Chemical 5]

[Chemical 6]

A fuel acetylene compound characterized by having a structure represented by:

[12] A polyacetylene derivative obtained by polymerizing the phenylacetylene compound according to claim 11.

[13] By deprotecting a polyphenylacetylene derivative having a structure in which a hydroxyl group or amino group bonded to a phenyl group is protected with a substituent, the following general formula (III)

[Chemical 7]

Comprising a step of producing a polyacetylene derivative represented by the formula: A method for producing a phenylacetylene derivative.

The following general formula (IV)

[Chemical 8]

(Where R ⁴ is

[Chemical 9]

Or

[Chemical 10]

And n is an integer of 10 or more. )

By deprotecting the polyacetylene derivative having the structure represented by the following general formula (ΠΙ)

[Chemical 11]

A process for producing a polyacetylene derivative represented by the formula:

[15] The method for producing a polyacetylacetylene derivative according to [14], further comprising the step of producing a polyacetylene derivative having a structure represented by the general formula (IV).

[16] The polyphenylacetylene derivative according to [14] or [15], further comprising a step of forming a film of the polyacetylene derivative having the structure represented by the general formula (IV). Production method.

[17] The polyphenylacetylene derivative according to [15] or [16], wherein a rhodium catalyst is used in producing the polyphenylacetylene derivative having the structure represented by the general formula (IV). Manufacturing method.

[18] The rhodium catalyst is [Rh (nbd) Cl], and KN (SiMe) is used as a cocatalyst.

2 3 2

The method for producing a polyphenylacetylene derivative according to claim 17, wherein