JPH0413650A - Diphenyldiacetylenic tetracarboxylic acid ester - Google Patents

Abstract

NEW MATERIAL:A diphenyldiacetylenic tetracarboxylic acid ester expressed by the formula (R1 to R4 are 1-24C monofunctional hydrocarbon group). USE:Useful as high-elastic modulus materials, thermochromic materials, nonlinear optical materials, etc., and extremely useful for synthesizing various diphenyldiacetylenic compounds. PREPARATION:4-Ethynylphthalic acid or 4-ethynylphthalic acid anhydride is esterified according to a conventional method and then reacted with one or two ester compounds. Thereby, the ethynyl groups are coupled to afford the compound expressed by formula I. The esterification is carried out by using a method for directly reacting the 4-ethynylphthalic acid with a compound expressed by the formula ROH (R is same as R1 to R4) having the objective hydrocarbon group, etc., if, e.g. the same hydrocarbon groups are introduced into two carboxyl groups on one phenyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to diphenyl diacetylene tetracarboxylic acid esters having excellent solid phase polymerizability. More specifically, it relates to diphenyl diacetylene tetracarboxylic acid esters useful for high elastic modulus materials, nonlinear optical materials, thermochromic materials, etc., and very useful for synthesizing various diphenyl diacetylene compounds. be.

[Conventional technology]

Due to their conjugated structures, diacetylene compounds and their polymers are being developed as nonlinear optical materials, conductive materials, thermochromic materials, and high-modulus materials.

When we look at the chemical structures of these diacetylene compounds, we find that diacetylene compounds with a diphenyl diacetylene structure in their main skeleton are the most excellent materials in terms of conjugated length, rigidity, heat resistance, etc. Possible. However, unsubstituted diphenyl diacetylene does not exhibit topochemical solid phase polymerization under normal conditions. Therefore, efforts are being made to improve solid phase polymerizability by introducing various substituents onto the phenyl group.

[Problems to be Solved by the Invention] However, not many diphenyl diacetylene compounds that undergo solid phase polymerization have been known, and most of them have low solid phase polymerizability or are solid phase polymerizable. Examples of diphenyl diacetylene compounds include trifluoromethyl groups (Polym, Prep-rlnj, +Jpn,
+ Peeling, 2491 (1984) ) and amide groups (
Polym, Preprint, Jpn, 33
Although nuclear-substituted diphenyl diacetylene compounds are known, they are difficult to synthesize and do not necessarily have high solid-state polymerizability, and they have high polymerization under mild conditions. Synthesis of diphenyl diacetylene compounds that can achieve solid phase polymerization and high polymerization yields is required from the viewpoint of material development.

[Means to solve the problem]

In order to solve this problem, the present inventors have synthesized various diphenyl diacetylene compounds and investigated their solid phase polymerizability. As a result, each phenyl group has 2
It was discovered that a diphenyl diacetylene compound having ester groups has the possibility of exhibiting excellent solid phase polymerizability, and furthermore,
As a result of intensive studies on the types of substituents, solid phase polymerization conditions, etc., the present invention was achieved. That is, the present invention provides a diphenyl diacetylene tetracarboxylic acid ester having the following general formula.

(Here, R3, Rt, R3, and R4 represent monovalent hydrocarbon groups having 1 to 24 carbon atoms.) In the present invention, R1, R,, R, and R4 have 1 to 24 carbon atoms. Represents up to 24 monovalent hydrocarbon groups of the same or different types.

Examples include -CH3, -CHzCH8, -CHzCF
IzCHz, -ecH! -) TCH3, f'CHz? a
cFIs, -ecFI2hcL, -ecH2mH3
fcTz+TcFls, 10z 'rr'r CH
3. ℃El z nide + acHs, -KHzYT
linear and branched aliphatic hydrocarbon groups, such as
Further, it may contain a hydrocarbon group having a carbon-carbon unsaturated bond such as a double bond or a triple bond.

When used as a high elastic modulus material and its raw material, R8, RI R1, and R1 should be small (one is a hydrocarbon group with a small molecular weight, such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.). The number of low molecular weight hydrocarbon groups is preferably as large as possible, and it is particularly preferred that all of the low molecular weight hydrocarbon groups are low molecular weight hydrocarbon groups.

Most preferably, any or all of R1,6, R1, and R4 is a methyl group.

When used as intermediate raw materials for synthesizing various diphenyl diacetylene derivatives, R6, R2, R1, R
It is desirable that at least one of 4 is a primary hydrocarbon group, and the smaller the molecular weight of the hydrocarbon group, the more preferable it is. In particular, when there are two low-molecular primary hydrocarbon groups, it can be derivatized and used, for example, as a raw material for polymer synthesis. In this case, the two may be attached to R1 and R2, or R1 and R4, or either R1 and R1 and either R3 or R4 may be attached. In the latter case, the synthesized polymer becomes linear and more rigid. Also 4
When all of the alkyl groups are low-molecular primary hydrocarbon groups, the synthesis of the acid anhydride becomes easy.

When R,, uz, R8, and R4 are secondary or tertiary, they are stabilized against hydrogenolysis, ammonolysis, alkaline hydrolysis, etc. Specifically, if one carbonyl group attached to a secondary or tertiary hydrocarbon group is attached to each phenyl group, the other carbonyl group attached to the same phenyl group can also be resistant to hydrolysis, etc. ,
Therefore, it is particularly preferable that each phenyl group has at least one carbonyl group having a secondary or tertiary hydrocarbon group, since this increases the hydrolysis resistance of the compound itself. The compounds R1 and R2 themselves have high hydrolysis resistance, and are particularly preferred.

When used as a functional material by utilizing thermochromic phenomenon, nonlinear optical phenomenon, etc., it is stable against heat and
It is desirable that the molecular movements of R+, Rz, R1, and R4 change due to heat. In this case, it has a large number of carbons, 0%
The above hydrocarbon groups are preferred.

Any branched hydrocarbon group may be used, but preferably a long linear aliphatic hydrocarbon group is R1+ Rz, R,, R4
In 1,000CH,+TCH3, 1 is 4 or more, especially 7
The above is preferable, and when an alicyclic group is included, n is preferably 5 or more.

When used in thermochromic materials, the number of long-chain aliphatic hydrocarbon groups to be included can be selected depending on the purpose in order to control color change due to temperature, but in general, two long-chain aliphatic hydrocarbon groups are used. When containing a chain aliphatic hydrocarbon group, R1
, R2, R1, and R4 each preferably contain one long-chain aliphatic hydrocarbon group, and those containing long-chain aliphatic hydrocarbon groups in all four groups have a lower temperature This is useful because it allows a region to exhibit a color change depending on temperature.

Further, depending on the selection of R1, R2, R1, and R1, the tetracarboxylic acid ester of the present invention can have an asymmetric molecular structure. Such an asymmetric structure can impart unique chemical, electrical, and optical properties to the compound, and is a preferred compound in the present invention. An asymmetric structure occurs in the case of R1×R1 and/or Rz×R4. In these cases, it is preferable that the different hydrocarbon groups have extremely different properties; for example, one is a short-chain hydrocarbon group (methyl group, ethyl group, propyl group, etc.) and the other is a long-chain hydrocarbon group. chain hydrocarbon group, -+cHz)7-C11s (j! is 5
By combining comrades with the above-mentioned properties, various interesting properties can be expressed.

In addition, if one of R, R, R3, and R4 has a hydrocarbon group containing an alicyclic group or an aromatic group, it has excellent heat resistance. Heat resistance is improved compared to when only the group is replaced with a group.Among these, -CHt-(
) A group containing an aromatic group such as these is particularly preferred. Further, the more hydrocarbon groups including alicyclic groups and aromatic groups are included, the higher the heat resistance is. In particular, the case where all of the hydrocarbon groups include aromatic groups has the highest heat resistance.

In the present invention, the hydrogen groups in Ro, R2, R1, and R4 are substituted with other groups, such as halogen, alkoxy group, amino group, carboxyl group, sulfonyl group, nitro group, and trifluoromethyl group. Even if it is, there is no particular problem as long as it does not interfere with solid phase polymerization.

In the present invention, even if the hydrogen group in the general formula is substituted with another group, such as a halogen, amino group, carboxyl group, alkoxy group, sulfonyl group, nitro group, or trifluoromethyl group, There is no particular problem as long as it does not interfere with phase polymerization.

The tetracarboxylic acid esters of the present invention are 4-ethynyl phthalic acid and 4-ethynyl phthalic anhydride (J, Org
,cheap,, 4fi, 5135 (198
3) It can be synthesized by deriving from ). That is, after esterifying 4-ethynyl phthalic acid or 4-ethynyl phthalic anhydride by a conventional method, 1
The desired tetracarboxylic acid ester can be obtained by reacting a species or two types of ester compounds and coupling the ethynyl groups. To describe each step more specifically, in the esterification step, when introducing the same hydrocarbon group into two carboxyl groups on one phenyl group, 4-ethynyl phthalic acid and the target hydrocarbon R with a group
A method of directly reacting with an alcohol or phenol represented by OH (where R is a hydrocarbon group corresponding to R1+ Rz, Ra, R4) - First, using thionyl chloride etc. to form a halide, and then Examples include a method of reacting with alcohol or phenol, and a method of directly reacting 4-ethynyl phthalic anhydride with the alcohol or phenol.

Moreover, when introducing different types of hydrocarbon groups into the same phenyl group, first, only one is esterified, and then the other carboxyl group and the different types of hydrocarbon groups are reacted.

At this time, the first stage reaction is obtained by adding a small amount of p-toluenesulfonic acid as a catalyst to the usual esterification method. After that, the remaining carboxyl groups are esterified, but the reaction at this time can be carried out by selecting more severe reaction conditions in the usual esterification method, or by first reacting the remaining carboxyl groups with thionyl chloride etc. After halogenation, it is reacted with an alcohol or phenol or a metal salt of R-ONa such as R-OK. The latter has a higher yield.

As a coupling method for an ethynyl group when synthesizing the tetracarboxylic acid ester of the present invention, a conventional coupling method for an ethynyl group can be used. For example, when coupling ester compounds of the same type,
This method according to the following reaction formula is a method for oxidatively trimerizing an ethynyl compound. The number of moles of the metal catalyst used in this reaction is preferably 0.01 to 1 equivalent relative to the substrate, and the flow rate of oxygen is preferably 10 to 1000 Id/win.

As the solvent used in this reaction, pyridine is preferable,
It is also possible to coexist other solvents.

The reaction temperature is preferably between -20°C and 100°C, and more preferably between 0°C and 70°C, since ethynyl groups may react if the reaction temperature is too high. The reaction time is not particularly limited, but is preferably in the range of 5 minutes to 12 hours.

In addition, when oxidatively coupling different types of ester compounds, one of the ethynyl compounds is halogenated, particularly preferably brominated, and a coupling reaction between the ethynyl compound and the ethynyl halide is performed as shown in the reaction formula below. Can be synthesized. This reaction is generally performed by adding an ethynyl halide to a solution of a compound having an ethynyl group in the presence of an amine (e.g. n-butylamine) as a catalyst, a metal salt such as cuprous chloride, and a small amount of hydroxylamine. This is done by adding gradually while stirring. The amount of cuprous chloride used is 1 to 5% as a molar ratio to suppress side reactions.
is preferred.

The structure of the tetracarboxylic acid ester obtained by the above method can be determined by general-purpose instrumental analysis means such as TR spectrum, NMR spectrum, and mass spectrum.
It's easy to do.

The polymer obtained by reacting the diacetylene group of the tetracarboxylic acid ester of the present invention can be prepared by heating, pressurizing, or irradiating the diacetylene group of the tetracarboxylic acid ester as a monomer with high-intensity radiation such as light irradiation, electron beam, gamma ray, etc. It can be synthesized by reaction using excitation means such as energy irradiation.

This reaction method can be carried out by selecting appropriate conditions by applying existing reaction methods for diacetylene groups disclosed in JP-A-62-267279 and JP-A-1-108204. The crosslinked product obtained in this way generally has lower solubility in solvents and meltability when heated, and in many cases becomes insoluble, but some long-chain esters In some cases, a transition temperature is observed. The chemical structure of the polymer includes the following en-yne structure when the diacetylene group undergoes a solid phase topochemical reaction.

On the other hand, when the polymer causes a random polymerization reaction of diacetylene groups, the structure of the polymer can generally be specified by
It will be extremely difficult. However, whether or not diacetylene groups have reacted can be determined by the decrease in diacetylene groups before and after the reaction. The reduction of diacetylene groups due to reaction can be easily determined by general-purpose instrumental analysis methods such as TR spectra, solid-state NMR spectra, and Raman spectra.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained with reference to examples, but the present invention is not limited to the following examples.

Reference example J, Org, Che+m, 48, 5135
(1983).

1.2 m of 4-ethynyl phthalic anhydride synthesized according to
oj! was dissolved in 1.51 methanol and heated under reflux for 10 hours in the presence of a catalytic amount of sulfuric acid. After distilling off the methanol, the residue was dissolved in ether, and the ether solution was mixed with a dilute aqueous sodium hydroxide solution. After washing with water, it was dried with boron's salt. Thereafter, the ether was distilled off to obtain the desired product as a colorless viscous oil. Yield 95%.

Synthesis and polymerization of Example 1 5+wmol of cuprous chloride was dissolved in 20d of pyridine at 30%
The mixture was stirred at °C for 3 hours while bubbling oxygen.

After the reaction, the precipitated solid was isolated by suction filtration and repeatedly recrystallized from methanol. Compounds were identified by means such as IR spectra, NMR spectra, and elemental analysis.

IR (cm-ri: 2950.1728.1600.
When the obtained target product of 1435.1293 was irradiated with γ-rays at 100 MRad, a black insoluble and infusible polymer was obtained with a yield of 85%. The elemental analysis value of the obtained polymer was the same as the elemental analysis value of the monomer within the range of error. Moreover, its Raman spectrum revealed that its main chain structure was an en-yne structure.

Synthesis and polymerization of Example 2 The reference example was repeated except that methanol was replaced with ethanol, and a colorless viscous oil-like Example 3 1st $ii5wmoj! in pyridine 30M1 at 30°
The mixture was stirred at C for 3 hours while bubbling oxygen. After the reaction, the precipitated solid was isolated by suction and repeatedly recrystallized from methanol. Compounds were identified by means such as IR spectra, NMR spectra, and elemental analysis. Yield 93% IR (ell-Otori): 28
90, 1728, 1602, 1367, 1294 When the obtained object was irradiated with 100 MRadOT rays,
A black, insoluble, infusible polymer was obtained with a yield of 70%.

The elemental analysis value of the obtained polymer was the same as the elemental analysis value of the monomer within the range of error. Furthermore, the existence of an en-in structure was revealed from the lamanthus vector.

Synthesis and polymerization A colorless viscous oil was obtained by repeating the reference example except that methanol was replaced with isopropyl alcohol. Yield 80% and #1 chloride! 10+a+oj! in 50d of pyridine,
The mixture was stirred at 30°C for 3 hours while bubbling oxygen. After the reaction, the precipitated solid was isolated by suction, and then
Repeated recrystallization from methanol was performed.

Compounds were identified by means such as IR spectra, NMR spectra, and elemental analysis.

Yield 80% Summer RCa mouth +-'): 2863, 1729,
1476, 1290 The obtained target product was reacted at 100°C for 5 hours to perform solid phase polymerization, and a black insoluble and infusible polymer was obtained in a yield of 45%. The elemental analysis value of the obtained polymer was the same as the elemental analysis value of Senzuma within the range of error. Moreover, the existence of an en-yne structure was revealed from its Raman spectrum.

Moreover, the obtained product had excellent resistance to solvents.

Example 4 When the obtained target product was irradiated with 80 MRadOT radiation, a black polymer was obtained with a yield of 45%.

The elemental analysis value of the obtained polymer was the same as the elemental analysis value of Nanatsumer within the range of error. The Raman spectrum also revealed the existence of an en-yne structure.

Synthesis and polymerization of Example 5 The desired product was obtained in the same manner as Reference Example and Example 1, except that propyl alcohol was used instead of methanol.
Yield 63% IR(am-'): 2905.1728.16
02.1388.1293 An experiment similar to Reference Example and Example 1 was conducted except that methanol was replaced with hexanol. The yield of the synthesized monomer was 80%.

IR(C1l-'): 2879.1730.1
601.1381.1248 The polymer obtained was purple in color and with a yield of 70%.

Example 6 Example 7 The desired product was obtained in the same manner as Reference Example and Example 1 except that methanol was replaced with dodecyl alcohol.

Yield 84% IR (cm-'): 2850.1743.144
0.1240.1052 80MRad to the obtained object
When irradiated with OT rays, a purple polymer was obtained with a yield of 45%. The elemental analysis value of the obtained polymer was the same as the elemental analysis value of the monomer within the range of error. Also,
The Raman spectrum revealed the existence of an en-yne structure.

In the following margin, add 0.5111 ol of 4-ethynyl phthalic anhydride to 1 j of dodecyl alcohol! and heated under reflux for 10 hours in the presence of a catalytic amount of p-)luenesulfonic acid. After the reaction, dodecyl alcohol was distilled off, and the residue was dissolved in ether.
The ether solution was washed with a dilute aqueous sodium hydroxide solution and pure water, dried over sulfur salt, and then the ether was distilled off to obtain a pale orange solid. Then, weigh out 100g of this solid,
Dissolved in hexanol 500- in the presence of a catalytic amount of sulfuric acid,
After reflux heating for 10 hours, the hexanol was distilled off, the residue was dissolved in ether, the ether solution was washed with a dilute aqueous sodium hydroxide solution and pure water, and dried over sulfur salt.Then, the ether was distilled off to form an oil. I got it.

30g of the obtained oil and 4500cm of No.1 chloride (5mm
off) was stirred in 200°C of pyridine at 45°C for 3 hours while bubbling oxygen. After the reaction, the precipitated solid was isolated by suction and repeatedly extracted from methanol.
Recrystallization was performed. Fixation of compound, IR spectrum, N
This was done by means such as MR spectroscopy and elemental analysis.

IR (cm-'): 287B, 2850.17
30.1381.1240 80 MRa to the obtained target product
When T-ray irradiation was performed, the black polymer was 35%
was obtained in a yield of . The elemental analysis values of the obtained polymer are as follows:
The elemental analysis values were the same within the margin of error as for Nanatsuma. Moreover, the existence of an en-yne structure was revealed from its Raman spectrum.

Synthesis and Polymerization of Example Day 4-ethynyl phthalic anhydride Q, 5mof was dissolved in methanol 11 and heated under reflux for 12 hours or more in the presence of a catalytic amount of p-toluenesulfonic acid. After the reaction, methanol was distilled off, the residue was dissolved in ether, the ether solution was washed with a dilute aqueous sodium hydroxide solution and pure water, and dried over sulfur salt.The ether was distilled off to obtain a pale orange solid. Obtained. Thereafter, 50 g of this solid was weighed, and thionyl chloride 2
00 and heated under reflux for over 5 hours. After the reaction, thionyl chloride was completely distilled off, and then ethanol, 300-
A catalytic amount of sulfuric acid was added thereto, and the mixture was heated under reflux for 5 hours or more under a nitrogen stream. After the reaction, ethanol is distilled off, the residue is dissolved in ether, the ether solution is washed with a dilute aqueous sodium hydroxide solution and pure water, and dried over sulfur salt.Then, the ether is distilled off to obtain the desired product. Obtained. Yield 63% IR(am-'): 2950.2890.17
30.1600.1294 The obtained object is exposed to ultraviolet light (
254 nm) for 12 hours, a black polymer was obtained at a rate of 30%. The elemental analysis value of the obtained polymer was the same as the elemental analysis value of Nanatsumer within the range of error. Moreover, the existence of an en-yne structure was revealed from the Raman spectrum.

Synthesis and polymerization of Example 9 The reference example was repeated except that dodecyl alcohol was used instead of methanol, and 2.5 mmoe of cuprous chloride, NH
zoll 5.45 d (0,32 ae) and n-
The desired product was obtained by reaction in the presence of 20 mft of butylamine.

Yield: 52% Compound immobilization was performed using IR spectrum, NMR spectrum,
This was done by means such as elemental analysis.

I R (cm-'): 2950.2850.17
30.1600 The obtained target product is exposed to ultraviolet g (254n
m) was irradiated for 24 hours, the black polymer was 44
% yield. The elemental analysis values of the obtained polymer were the same as the monomer elemental analysis values within the margin of error.

Moreover, the existence of an en-yne structure was revealed from its Raman spectrum.

Example 10 Obtained from the reaction at the bottom left.

Reference Example and Example 1 were repeated using nonyphenol instead of methanol to obtain the desired product.

Yield 73% IR(C11-'): 2920.2854.17
10.1603.1212 The obtained object is 150'
When heated at C for 10 hours to perform face phase polymerization, a purple polymer was obtained.

Example 11 was conducted by means such as IR spectroscopy, NMR spectroscopy, and elemental analysis. Yield 82%IR(cl'
):2930.2879.1725.1603.124
8.119019 The obtained target product was subjected to solid phase polymerization by heating at 150° C. for 110 hours, and a black polymer was obtained in a yield of 70%. Moreover, the existence of an en-yne structure was revealed from its Raman spectrum.

In addition, this nanatsuma has excellent heat resistance and has a heat resistance of 250
No decomposition occurred even after heating at ℃ for 5 minutes.

Example 12 3 ms+o 1 of copper was dissolved in 50 III of pyridine,
The mixture was stirred at 50°C for 5 hours while bubbling oxygen. After repulsion, the precipitated solid was isolated by suction filtration and repeatedly recrystallized from methanol. Synthesis and Polymerization of Compound Identification 5 mmon of cuprous chloride was dissolved in 50 mL of pyridine.
The mixture was stirred at °C for 5 hours while bubbling oxygen.

After repulsion, the precipitated solid was isolated by suction filtration and repeatedly recrystallized from methanol. Compounds were identified by means such as IR spectra, NMR spectra, and elemental analysis. Yield 93%IR(C11-')
: 2923.1725.1605.1250.119
6 The obtained target product was heated at 170"C for 5 hours to perform solid phase polymerization, and a black polymer was obtained in a yield of 30%. Also, from the ramance vector, en-in In addition, this monomer has excellent heat resistance and did not decompose even when heated at 250°C for 5 minutes.

Synthesis and I of Example 13 0.2 raol of 4-ethynyl phthalic anhydride and 0.6 moA of stearyl alcohol were heated under reflux for 10 hours in a benzene solvent in the presence of a catalytic amount of sulfuric acid. After the reaction, the stearyl alcohol was distilled off, the residue was dissolved in ether, the ether solution was washed with a dilute aqueous sodium hydroxide solution and pure water, dried over sulfur salt, and then the ether was distilled off. The obtained cuprous chloride 1, Ommol pyridine 100r
The mixture was stirred for 3 hours at 30°C while bubbling oxygen. After the reaction, the precipitated solid was isolated by suction filtration.

IR(am-'): 284B, 1764.16
03.1360.1185 The obtained target product was heated to 150°C.
When heated for 10 hours to perform face phase polymerization, a purple polymer was obtained in a yield of 37%. Furthermore, the existence of an en-yne structure was revealed from the Raman spectrum.

〔Effect of the invention〕

The tetracarboxylic acid ester of the present invention is a compound that is relatively easy to synthesize and has high solid phase polymerizability, and can be used together with its polymer for high elastic modulus materials, thermochromic materials, nonlinear optical materials, etc. . Moreover, it is very useful for synthesizing various diphenyl diacetylene derivatives, and is useful for developing new diacetylene compound materials.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] 1. A diphenyl diacetylene tetracarboxylic acid ester having the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R_1, R_2, R_3, R_4 represent monovalent hydrocarbon groups with carbon numbers from 1 to 24.)