JPH03294261A - Diacetylene based sulfide ester and polymer thereof - Google Patents

Abstract

NEW MATERIAL:A diacetylene based sulfide ester expressed by formula I (R is 1-7C monovalent aliphatic, aromatic or alicyclic hydrocarbon group; A is H or methyl; Z is 1-12C divalent aliphatic, aromatic or alicyclic hydrocarbon group). EXAMPLE:A compound expressed by formula II. USE:The compound expressed by formula I is a monomer having high solid reactivity and a polymer obtained therefrom has extremely excellent heat resis tance and is useful as a raw material for nonlinear optical material, conductive material, high-modulus material, composite material, etc. PREPARATION:As shown in the reaction formula, diacetylene ester is reacted with a thiol in a solvent such as hexane in the presence of a base such as tert. butyl-lithium, sodium carbonate, etc. at -30 deg.C to 300 deg.C to provide the compound expressed by formula I. A molar ratio of the diacetylene ester to base is 0.2-0.5, preferably 1.05-0.95.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to diacetylene sulfide esters and polymers thereof, and more specifically, diacetylene sulfide esters with excellent polymerizability and polymerization reactions thereof. This relates to a polymer of 85 diacetylene compound obtained by.

(Prior Art) In recent years, many diacetylene compounds having ester groups have been synthesized, and their solid phase polymerizability has been studied. this is,
This is because ester diacetylene compounds can be synthesized relatively easily from the corresponding carboxylic acid derivative and alcohol. Furthermore, since these raw materials are relatively inexpensive, they are considered to be industrially promising from the viewpoint of manufacturing costs.

(The problem that the invention is trying to solve) However,
It has been reported that ester-based diacetylene compounds generally have low solid phase polymerizability; for example, L6-bis(
Capryloxy)-2,4-hexadiyne is known to undergo solid phase polymerization with a yield of several percent only by ultraviolet irradiation. If an easily synthesized ester-based diacetylene compound with excellent solid-phase polymerizability could be obtained, a variety of applications could be expected, but at present such ester-based diacetylene compounds have hardly been found. Not yet.

Moreover, the heat resistance of the polymer of the -m-type ester diacetylene compound is not necessarily sufficient.

(Means for Solving the Problem) In order to solve the problem, the present inventors synthesized various diacetylene compounds, and as a result, a diacetylene compound having an α,β-unsaturated ester moiety was synthesized. We have discovered that diacetylene compounds produced by Michael addition reactions of thiols exhibit high reactivity and have the potential to yield polymers with high polymerization rates. Furthermore, as a result of intensive studies on the bonding mode between the diacetylene group and the functional group, the type of thiol, reaction conditions, etc., the present invention was achieved.

That is, the present invention provides a diacetylene sulfide ester having the following structural formula and a polymer thereof.

R5CHZCHCOOZCmiCC=CZOOCCHCH
zSR^ A (Here, R is a monovalent aliphatic, aromatic, or alicyclic hydrocarbon group having 1 to 7 carbon atoms, A is a hydrogen atom or a methyl group, and Z is 2 having 1 to 12 carbon atoms. Value of aliphatic, aromatic,
(represents a hydrocarbon group) In the present invention, R represents a monovalent aliphatic, aromatic, or alicyclic hydrocarbon group having 1 to 7 carbon atoms, examples thereof include -CH1-CHzCHi, -CHzCHzCHi , −
CHzCHzCToCHs.

-CHzC)IzCLCHzCL, -CHzC)I
zC)IzC)IzGHzCH3ICH.

Among these R, in order to improve the polymerizability of the diacetylene group, -CHt, -CHzCHs, -CHzCH
zCHi.

-CHzCHzCHtCHzCtbCH3 is preferred,
In the obtained poly in the present invention, Z has 1 to 12 carbon atoms.
Examples of divalent groups include -C)tz-, -C)IzCHz-, -CHzCHzC
Published by Hz-, -f-CH2.

Among these Zs, -CH,-, -CHzCHz-1-CHzCHzCHz
-1÷CH2+T- is preferable to improve the heat resistance of the obtained polymer. In the present invention, A represents a hydrogen atom or a methyl group, but from the viewpoint of increasing the phase polymerizability of the diacetylene group, a hydrogen atom is preferable. , Further, from the viewpoint of low manufacturing cost, a methyl group is preferable.

Examples of the diacetylene sulfide ester of the present invention include the following structural units.

C1hSCH2C)12C00C)12C3CC3CC
)1200CCHICH! 5CH3C)13 (CL)
tscHzcHzcOOcHzC=cC=CCH□0
0CCHzCHzS(CHz)CHzC)Igo(CHri) 5scl(tcHzcOo(C)lx) 6CmiCC
=C (CHz) ,0OCCHtCHffiS (CL
) SCH.

Margins below The diacetylene sulfide ester of the present invention can be synthesized using known organic synthesis reactions, and the synthesis method is not particularly limited, examples include the synthesis method shown by the following reaction formula. .

This synthesis method is a method in which a diacetylene ester and a thiol are reacted in, for example, a general-purpose solvent. in this case,
A preferred method is to convert the thiol into a thiolate anion in-system and then add it to the double bond. Therefore, a method using a base to generate a thiolate anion is preferable for this addition reaction. The base used is
t-butyllithium, 5ec-butyllithium, Grignard reagent, pyridine, triethylamine, sodium methylate, sodium ethylate, potassium methylate,
Potassium ethylate, lithium diisopropylamide,
Examples include sodium carbonate, potassium carbonate, potassium hydroxide, and sodium hydroxide. The molar ratio of diacetylene ester to base is from 2 to 0.5, preferably from 1.2 to 0.8 to increase the yield, more preferably from 1.05 to 0.95.

The molar ratio of the diacetylene ester component to the sulfide component is 2 to 0.5, and is 1.2 to increase the yield.
The color is 0.8, more preferably 1.05 to 0.95. Examples of solvents include hexane, benzene, toluene, chloroform, trichlene, acetone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, water, etc.The heat of reaction is small and it is easy to decompose during synthesis. If there are no such problems, there is no need to use a solvent.

If necessary, an inorganic salt, a catalyst, or a second or third solvent may be dissolved or mixed before use.

The amount of solvent is not particularly limited, but is preferably 0.01 to 100 g per 1.0 g of sulfide, and from 0.1 to 50 g in consideration of reaction efficiency and cost reduction. There is no particular limit, but from 10 seconds to 1
0 hours, preferably 1 hour to increase reaction efficiency.
It is from 0 seconds to 5 hours.

There is no limit to the reaction temperature, but it is generally -30 to 300°C.
℃, and if the reaction is too vigorous, cooling or other measures may be taken as necessary.

In addition to the synthesis method exemplified here, for example, a method in which an α,β-unsaturated ester having an ethynyl group is previously subjected to a Michael addition reaction with a sulfide, and the resulting amino ester is subjected to an oxidative camping reaction to obtain the desired product is also available. Excellent from the point of view.

The purity of the diacetylene sulfide ester obtained by the above method can be improved by general-purpose purification means such as recrystallization, chromatography, and distillation, if necessary. In addition, the structure determination was performed using an IR spectrum,
This can be easily carried out using general-purpose instrumental analysis means such as NMR spectroscopy and mass spectroscopy.

The polymer obtained by reacting the diacetylene group of the diacetylene sulfide ester of the present invention has the diacetylene group of the diacetylene sulfide ester that is the monomer,
It can be synthesized by reaction using excitation means such as heating, pressurization, or high-energy light irradiation. The polymer thus obtained contains the following en-yne structure as a result of a solid-phase topochemical reaction of diacetylene groups.

Below Margin ZOOCCHzC)ISR = Cow c-c=c-c→= A ZOOCCH2CI(SR On the other hand, if the polymer is produced by a random crosslinking reaction of diacetylene groups, the structure can be specified by boat fishing. However, whether or not the diacetylene groups have reacted can be determined by the decrease in diacetylene groups before and after the reaction.The decrease in diacetylene groups due to the reaction can be determined by IR spectra, solid-state NMR spectra, and Raman spectra. This can be easily determined using general-purpose instrumental analysis methods such as .

Examples of reaction means for the diacetylene group include heating, pressurization, and excitation means such as high-energy light irradiation.
Existing reaction methods for diacetylene groups can be used as is. As such a reaction method, for example, the methods disclosed in JP-A-62-267279 and JP-A-1-108204 can be applied as they are.

(Effects of the Invention) The diacetylene sulfide ester of the present invention is a monomer that is inexpensive and has high solid phase reactivity. Furthermore, the obtained polymer has excellent heat resistance and is extremely useful as a raw material for nonlinear optical materials, conductive materials, high elastic modulus materials, composite materials, and the like.

(Examples) The present invention will be described below with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples.

(Example 1) CJ? 5CHHzCH2COOCHzC=CC=CCHz
oOccHzCH2SC3H synthesis and polymerization 1,6-diacryloyl-2,4-hexadiyne 100
mmol 250 mmol of n-propylthiol, 25 Ommol of sodium hydroxide, 20 m of N,N-dimethylacetamide! The mixture was stirred at 80°C for 1 hour.

After the reaction, the solvent and excess thiol were distilled off under reduced pressure, and the residue was washed with dilute hydrochloric acid and pure water. After the treatment, the residue was fractionated using silica gel chromatography and purified by recrystallization from hexane. Compounds were identified by means such as IR spectra, NMR spectra, and elemental analysis.

Yield 58% IR(cl'): 2986.1738.153
0.1217.784 100MRad to the obtained target
When T-ray irradiation was performed, a red insoluble and infusible polymer was obtained in a yield of 56%. The elemental analysis values of the obtained polymer were the same as the elemental analysis values of the monomer within the margin of error. Furthermore, the presence of double bonds was revealed from the IR spectrum. Also, the temperature at which weight loss starts is 309°C.
It was good.

(Example 2) Synthesis and polymerization 1,6-cymethacrylate-2,4-hexadiyne 10
0I100II1 and n-propylthiol 20 Omm
ol, t-butyllithium 2D Ommol was stirred in 20tn1 of chloroform at 30°C for 1 hour. After the reaction, the solvent was distilled off under reduced pressure. The residue was fractionated using silica gel chromatography, and then purified by recrystallization from hexane. Compounds were identified by means such as IR spectra, NMR spectra, and elemental analysis.

Acidity 82% IR (cm-'): 2989.2986.1738
．． 1530.1217° 100 MRa to the obtained target object
When irradiated with dOT rays, a red insoluble and infusible polymer was obtained in a yield of 69%. The elemental analysis values of the obtained polymer were the same as the elemental analysis values of the monomer within the margin of error.

Furthermore, the presence of double bonds was revealed from the IR spectrum. Moreover, the temperature at which weight loss started was 308°C, which was good.

(Example 3) C) IU CH.

Synthesis and polymerization of 1,6-dimethacrylate-2,4-hexadiyne 10
0gmo! 200 mmol of n-heptylthiol and 200 mmol of sodium methylate were stirred at 30°C for 1 hour in 20 volumes of toluene. After the reaction, the cuttings were distilled off under reduced pressure. After the residual aroma was separated by silica gel chromatography, it was purified by recrystallization from hexane. Identification of compounds is
This was carried out by means such as IR spectroscopy, NMR spectroscopy, and elemental analysis.

Yield 56% IR (cm-'): 2989.2986.173
B, 1530.1217° 100M to the obtained object
When Racl was irradiated with T-rays, a red insoluble and infusible polymer was obtained in a yield of 49%. The elemental analysis values of the obtained polymer were the same as the elemental analysis values of the monomer within the margin of error. Furthermore, the presence of double bonds was revealed from its IR spectrum. Also, the temperature at which weight loss starts is 30
The temperature was good at 7°C.

(Example 4) CJtSCHzcozcoo (CH2) 6Ci=
CC=C(C)I,) 100ccHzCHzSCJ
Synthesis and polymerization of ff Instead of 1,6-diacryl-1-2,4-hexadiyne, (CHz= Ct(Coo(Ct(z) hc=c
Example 1 was repeated except that ÷ was used. The target product was obtained with a yield of 79%.

I R(c'): 2977, 2956.1735
．． 1530.1218° When the obtained target product was heat-treated at 100°C for 12 hours, a red insoluble and infusible polymer was obtained with a yield of 24%. The elemental analysis values of the obtained polymer were the same as the elemental analysis values of the monomer within the margin of error. Furthermore, the presence of double bonds was revealed from the IR spectrum. Also, the temperature at which weight loss starts is 311°C.
It was good.

(Example 5) CdbSCHzCHzCOO(C)lz) r□CmiC
C=C(CHz) r z00ccHzcHzscJ7
Synthesis and polymerization of 1,6-diacrydo-2,4-hexadiyne instead of (C)It=CHCOO(C)lx) +zC-
Example 1 was repeated except using =C→T. The target product was obtained with a yield of 72%.

JR(c+o-'): 2967, 2946.
1738. 1534. 1222 The obtained target product was heat-treated at 100"C for 12 hours, and a red insoluble and infusible polymer was obtained with a yield of 39%. The elemental analysis value of the obtained polymer was the same as that of the monomer. The results were the same within the margin of error.The IR spectrum revealed the presence of double bonds.The temperature at which weight loss started was 312°C, which was good.

Example 6 Synthesis and Polymerization Example 1 was repeated except that 5ec-butylthiol was used instead of n-propylthiol.

The target product was obtained with a yield of 61%.

I R (cm-'): 29B7.2946.173
0.1530.1212 Ultraviolet light (25
When the polymer (4 nm) was heat-treated for 12 hours, a red insoluble and infusible polymer was obtained with a yield of 36%. The elemental analysis values of the obtained polymer were the same as the elemental analysis values of the monomer within the margin of error. Furthermore, the presence of double bonds was revealed from the IR spectrum. Moreover, the temperature at which weight loss started was 298°C, which was good.

(Example 7) CH, CH.

Synthesis and polymerization The experiment was repeated several times, except that 5ec-butylthiol was used instead of n-propylthiol.

The desired product was obtained with a yield of 26%.

I R (cm-'): 2933.1?32.153
4.1220.784Ultraviolet light (254
When the polymer (nm) was heat-treated for 12 hours, a red insoluble and infusible polymer was obtained with a yield of 64%. The elemental analysis values of the obtained polymer were the same as the elemental analysis values of the monomer within the margin of error. Furthermore, the presence of double bonds was revealed from the IR spectrum. Also, the temperature at which weight loss starts is 3
The temperature was good at 08°C.

(Example 8) ○SCH,C)IZCOO<I> CmiCC=CQ 0
Synthesis and polymerization of 0CCHzCHzS C) Iz=C) ICOO○C=CH 100 mmol, thiophenol 100 mmol, t-butyllithium 1
After 0 reaction, 00 mmol was reacted with 30 d of N,N-dimethylformamide at 100 °C for 1 hour.
The reaction product was poured into methanol, and the precipitated reaction product was isolated by suction filtration. Obtained sulfide ester 100
1 part and 1 part of copper(I) chloride were reacted in 500 parts of pyridine at room temperature for 5 hours while introducing oxygen gas. After the reaction, the precipitated solid was separated by filtration and repeatedly recrystallized from methyl ethyl ketone. . The target product was obtained with a yield of 56%.

IR (Koro): 3042.2936. 1732
．． 1620. When the obtained target product was heat-treated with ultraviolet light (254 parts m) for 12 hours, a red insoluble and infusible polymer was obtained in a yield of 32%. The elemental analysis value of the obtained polymer was the same as the elemental analysis value of Nanatsumer within the range of error. Furthermore, the presence of double bonds was revealed from its IR spectrum. Moreover, the weight loss starting temperature was 328"C, which was good.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] 1) A diacetylene sulfide ester having the following structural formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R is a monovalent aliphatic, aromatic, or alicyclic hydrocarbon group having 1 to 7 carbon atoms, A is a hydrogen atom or a methyl group, and Z is a carbon Divalent aliphatics and aromatics of numbers 1 to 12,
Indicates an alicyclic hydrocarbon group. )2) A polymer obtained by reacting the diacetylene group of the diacetylene sulfide ester described in claim 1.