JPH01108210A - Polydiacetylene having reacted double bond - Google Patents

Abstract

PURPOSE:To make it possible to produce a dense network polymer easily, by polymerizing the diacetylene group of a specific double bond-containing diacetylene compound, isolating the resulting double bond-containing polydiacetylene, and then reacting remaining double bonds. CONSTITUTION:The present polydiacetylene is produced by polymerizing the diacetylene group of a double bond-containing diacetylene compound having a monomer structure: R<1>-X-R<2>-CidenticalCCidenticalC-R<3>-X-R<4> (wherein R<1> and R<4> are each a monovalent organic group and at least one of R<1> and R<4> contains a double bond; X is an ester group or an amide group; and R<2> and R<3> are each a divalent organic group), and reacting the double bonds of the resulting polymer. Examples of the method of polymerizing the diacetylene group of the above double bond-containing diacetylene compound include photopolymerization, thermal polymerization and polymerization under pressure alone or in combination with each other. In order to react the remaining double bonds in the above groups R<1> and/or R<4> after the polymerization of the diacetylene group, the above method used in the polymerization of the diacetylene group is essentially applicable.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to polydiacetylene having a dense network polymer structure obtained by reacting the double bond portion of polydiacetylene containing double bonds. .

[Prior art]

In recent years, the synthesis of single-crystal polymers using topochemical reactions using diacetylene compounds has attracted attention, and attempts have been made to develop various functional polymers with high elastic modulus using this method.

The present inventors have already synthesized a novel diacetylene compound having a double bond, and have used this to develop various high-modulus polymer molded bodies.

[Problem to be solved by the invention] A compound having a double bond and a diacetylene group in the same molecule can be formed into a network polymer (with a diacetylene group and It is possible that the double bonds react independently to give a polymer with a chain-like molecular structure, but the production method is generally difficult, and unless conditions are chosen appropriately, the double bonds and diacetylene groups are simply random. Compared to randomly cross-linked polydiacetylene, which can only be obtained as a cross-linked polymer, polydiacetylene, which has a dense wire-like polymer structure, is highly crystalline and can be used as mechanical materials, conductive materials, etc.
It can be useful as an optical element.

[Means for solving the invention]

Therefore, in the process of investigating a method for obtaining a network polymer using diacetylene groups, the present inventors prepolymerized the diacetylene groups of a double bond-containing diacetylene compound,
Once the obtained double bond-containing polydiacetylene is isolated,
Next, we discovered that by efficiently reacting the remaining double bonds, a dense network polymer could be easily obtained.

Furthermore, the present invention was achieved as a result of intensive research into the bonding mode between double bonds and diacetylene groups, the types of organic groups Rm and R3 interposed between each functional group, etc. from the viewpoint of reactivity and synthesis.

That is, in the present invention, the structural formula of the monomer is R'-X-R
”-CmiCCmiC-R'-X-R' (where Rl,
R4 is a monovalent organic group, at least one of R1 or R4 contains a double bond, X is an ester group or an amide group, and R2 and R3 are divalent organic groups. ) The diacetylene group of the diacetin compound is prepolymerized and then the double bond is reacted to provide polydiacetylene.

In the monomer of the present invention, R1 and R' are monovalent organic groups, and at least one of R1 and R4 contains a double bond.

Examples of cases with double bonds include H, C=CI! "CI-, uzcushiC, CH2Cl-CH, CHt-CH
Cflg-2C(Ctls)z-CH,C(CH3)!
-C(CH3).

etc.

An example of a case without a double bond is CH3.

CH3 CH3G Hz O* (=)-GHz Hz-
etc. are mentioned. Furthermore, one or more hydrogen atoms of these monovalent organic groups R may be bonded to another bond, such as an ether bond,
Amino bond, ester bond, amide bond, imino bond,
It may be substituted with a nitro group, a halogen atom, etc.

Regarding the presence or absence of a double bond between R1 and R4, it is sufficient if at least one of them has a double bond, but in order to make the network of the network polymer more dense, R'.

It is preferable that both R4 contain a double bond.

X is an ester group or an amide group. In the case of an amide group, it may be either secondary or tertiary, but a secondary amide group is preferred in order to improve cohesive force due to hydrogen bonding. Further, in the case of a tertiary amide group, the organic group bonded to the nitrogen atom may be any organic group having the same structural formula as R1 or R4.

In the monomer of the present invention, R1 and R3 are divalent organic groups, examples of which include a complex group of an H3 group, an aliphatic group, and an alicyclic group,
In addition, some of the hydrogen atoms of these Rz and Rs are halogen atoms, nitro groups, hydroxyl groups, cyano groups, carboxyl groups, amino groups, amide groups, ester groups, carbonyl groups,
It may be substituted with an alkoxide group or the like.

In addition, the organic group may include an ether bond, a sulfonyl bond,
It may be an organic group connected by an amide bond, an ester bond, a carbonyl bond, etc., and to give specific examples of these, R1 and R3 are preferable because of their ease of synthesis and good heat resistance. -C1,+.

In order to improve the ease of formation and the reactivity of diacetylene groups, -CUZ-1 In order to improve heat resistance, -1-/7-R'-x-R"-c=CGIC-R3
To give a specific example of -X-R', CHz = CHC
NCHzCa CCiii CCHzNCCH= CH
zCH3CH-CHCNC)IICmiCCmiCCHJC
CH=CHCthCUt CHCIIzCH3 II HII CHz -CI(GOCHtCN CC'M CCHz
NCCH-CHzCHz-CHCOCHtCWCCIC
Examples include CHzOCCH=CHz, but it goes without saying that the present invention is not limited to these specific examples.

Monomer R'-X-R''-CmiCCmiC in the present invention
As an example of the synthesis method for -R3-X-R', when R'=R' or R"=R3 (7), R'-X-R"-C=CH is It can be synthesized by oxidative coupling using a metal catalyst and oxygen gas (G 1 a
s e r coupling).

On the other hand, in the case of R1-R4 or/and R''q&R3 (7),
It can be synthesized by halogenating the ethynyl hydrogen of R'-X-R''-C=i+CH and then oxidatively coupling it with R'-X-R'-C=CH using a metal catalyst such as copper acetate ( Cadiot-Chodkiewicz reaction), that is, according to the reaction formula as below (in the formula, H
al represents a halogen atom).

R'-X-R"-CaCH-R'-X-R"-C=CH
al R'-X-R''-C=CHal+R'-X-R'-Ca
cH-R1-X-R”-C=CCffiC-R”-X-
R' In the above synthesis examples, copper, manganese, or cobalt salts can be used as catalysts for the oxidative coupling reaction, and if necessary, co-catalysts such as tertiary amines and oximes may be allowed to coexist. As a metal salt, Cu Cl * Cu Cl
z + Cu I, Cu (00CCH3) z
+MnC1z +MnCO3, CoC1z, etc. can be used.

In the oxidative coupling reaction of the above synthesis example, the number of moles of the metal catalyst used is 0. It is preferable that 1 to 1 equivalent of O and the flow rate of oxygen be 10=1000 d/win.

Pyridine is preferred as the solvent used in this reaction, and other solvents may also be present.

There are no particular restrictions on the reaction temperature and reaction time, but preferably the reaction temperature is between -20°C and 100°C and the reaction time is 20 minutes to 12 hours.

In the above synthesis example, when halogenating the ethynyl hydrogen of R'-X-R"-C=CH, R'-X-R"-CI
It can be produced by reacting CH with sodium hypochlorite, sodium hypoiodine, sodium hypobromite, etc.

In the present invention, monomer R'-X-R"-C=ICC
For example, a method of prepolymerizing the diacetylene group of =IC-R'-X-R' is, for example, a monomer (R1-
In the photopolymerization method, UV irradiation using a low pressure, medium pressure, or high pressure mercury lamp,
It can be synthesized by polymerization using an electron beam irradiation method, a T-ray irradiation method, or a plasma polymerization method.

On the other hand, as a thermal polymerization method, for example, the monomer can be synthesized by heat-treating it for a certain period of time near the melting point or decomposition point of the monomer.

On the other hand, as a pressure polymerization method, it can be synthesized, for example, by subjecting monomers to pressure treatment under high pressure for a certain period of time.

When polymerizing diacetylene groups by the above method, the above photopolymerization method, thermal polymerization method, and pressure polymerization method may be used alone, but two or more may be used in combination. It is also possible to use a method of manufacturing the material, and this method is preferable.

In the above photopolymerization method, thermal polymerization method, and pressure polymerization method, polymerization accelerators such as peroxides, azo compounds, disulfide compounds, halogen compounds, and carbonyl compounds may be used.

Further, the system for polymerization may be any of bulk, solution, suspension, emulsion, and solid phase, but solid phase is particularly preferred.

In the case of solid phase polymerization, the monomer may be in the form of a powder, but is particularly preferably in the form of a single crystal.

In the above production method, in the case of photopolymerization method, the light source used,
There are no particular limitations on the output of the light source or the distance between the light source and the monomer, and there are no limitations on the reaction time either, but it is preferably from 1 second to 10 hours.

On the other hand, in the thermal polymerization method, the reaction temperature is not particularly limited, but is preferably 50°C below the melting point or decomposition point of the monomer.
The reaction time is from a low temperature to a melting point or a decomposition point, and there is no restriction on the reaction time, which is preferably from 10 minutes to 10 hours.

On the other hand, in the pressure polymerization method, the pressure is not particularly limited, but is preferably from 11,000 at to 110,000 at,
There is also no restriction on the reaction time, and the reaction time is preferably from 1 hour to 10 hours.

Next, after prepolymerizing the diacetylene group, in order to react the remaining double bonds of R1 and/or R4, basically the method used for polymerizing the diacetylene group, that is, photopolymerization method, thermal Polymerization method and pressure polymerization method can be applied, but the conditions used at that time must be sufficiently stronger than those used for polymerization of diacetylene groups to the extent that the sample does not decompose.For example, when thermal polymerization of diacetylene groups is If the temperature is 50''C, then the double bond reaction is carried out at a temperature of 100''C. To determine the treatment conditions for the double bond, thermal analysis, infrared spectroscopy, etc. can be used to find the conditions under which the double bond reaction occurs.

In addition, before the double bond reaction, the polydiacetylene in which diacetylene groups are polymerized is washed with a good solvent of an appropriate monomer to wash away the 7-mer and low molecular weight polydiacetylene contained in the polydiacetylene. It is possible, and even preferable.

In addition, when the double bond is reacted, infrared spectrum,
It is necessary to track the reaction using Raman spectroscopy, nuclear magnetic resonance spectroscopy, etc., and confirm the completion of the reaction.

The chemical structure of the polydiacetylene of the present invention can be analyzed using infrared spectroscopy, Raman spectroscopy, X-ray or electron diffraction, nuclear magnetic resonance, etc., but the polymerization of diacetylene groups is basically as described by G. Wegner et al. As proposed by (
Z, Neturforseh.

24b 824 (1969)), diacetylene group is 1
, 4-trans addition structure (formula ■) is shown.

On the other hand, regarding the structure of the double bond portion of R1 and/or R4, it is thought that a 1,2-addition reaction of the double bond occurs, but it is not necessarily limited to a 1,2-addition reaction. . Regarding the reaction of the double bond of R1 and/or R4, it is important that the double bond is not substantially detected in an infrared spectrum or the like.

Further, there is no particular restriction on the degree of polymerization of the double bond reacted with the polydiacetylene moiety, and it is sufficient as long as it is 2 or more.

〔Effect of the invention〕

The polydiacetylene of the present invention in which the double bond is reacted has a two-dimensional or three-dimensional dense network polymer structure because both the diethylene group and the double bond have reacted.
It also has a high degree of crystallinity and is useful as an organic filler that provides high two-dimensional or three-dimensional mechanical properties. It is also useful for imparting conductivity through doping and as a raw material for optical materials.

〔Example〕

Examples of the present invention are listed below, but the present invention is not limited to the following examples.

(Example 1) 11CHHz-CHCNCHZCyoCOO, 1 mole to 0.01
In the presence of molar CuC1, 301111! in pyridine,
The reaction was carried out at room temperature for 4 hours while introducing oxygen gas. After the reaction, the precipitated solid was isolated by suction filtration and recrystallized from hot water. The obtained monomer was white needle crystals.

The characteristic IR absorption of the monomer is shown below.

IR (KBr) 3238cm-', 3050C1-
'+1656CI11-'.

1624cm-'+ 1540C11-', 1245
aa-' DTA-TGA analysis of this monomer (20"C
When measured under a nitrogen stream at a temperature increase rate of /win), an exothermic peak due to polymerization of diacetylene groups was observed at 126°C, and an exothermic peak due to polymerization of olefins was observed at 156°C. Therefore, this monomer was subjected to thermal solid phase polymerization at 40 DEG C. for 20 hours and then at 170 DEG C. for 3 hours in a nitrogen atmosphere, and after the reaction was repeatedly washed with hot methanol, which is a good solvent for the monomer.

The obtained brownish-brown polymer is still acicular crystals,
The IR spectrum of the polymer after heat treatment at 40° C. for 20 hours was basically the same as the spectrum chart of the polymer, except for the absence of C-C absorption when compared with the IR spectrum.

(C=C absorption includes, for example, C-C stretching vibration near 1624C11-'.) I R(K
Br) 3238Cffi-'+ 1656C11-'l
1540CIm-'.

1245CIm-' [Example 2] CH3CH to CHCCI O, 1 mol.

1 mol of Na0HO was placed in 300 d of a mixed solvent of water-chloroform 1:1 and reacted at 0°C for 90 minutes.
After the reaction, the chloroform layer was concentrated and the residual aroma was recrystallized from N,N-dimethylacetamide.

The obtained crystals were white plate-like crystals.

The obtained solid was thermally polymerized at 130'C for 48 hours in argon, and further heated to 180°C and reacted for 24 hours. The resulting polymer was washed repeatedly with N,N-dimethylformamide. In heat treatment at 130°C, I
1600 CIm-' in R spectrum.

An absorption peak of C=C was observed at 932 cm-', but 2
After heat treatment at 80°C, their C═C absorption peak disappeared, and the other absorptions were basically the same as those after heat treatment at 130′C. Moreover, the obtained polymer was still a plate crystal.

I R (K Br) 3086cm-', 2978C1
1-'+ 1632C1! -'.

1536cm-' [Example 3] After irradiation with ultraviolet rays at -60°C for 50 hours under a nitrogen stream using a 256n+m ultraviolet lamp: The reactant was washed with acetone and further heated at 160'C for 5 hours. Heat treatment was performed under a nitrogen stream. Polymers obtained by heat treatment include
Based on the C-c stretching vibration observed before heat treatment <1602
The C11-' peak was not observed, and the other peaks were almost the same as before heat treatment.

Furthermore, there was no change in the crystal structure from microscopic observation.

IR(KBr)2963cm-', 1732C11
-'l 1230C1m-'.

11l100CI' [Example 4] Reaction was carried out at 30°C for 20 hours. After the reaction, chloroform was distilled off, and the residual aroma was recrystallized from acetone.

The needles thus obtained were heat treated at 180'C for 3 days in argon and further heat treated at 250'C for 5 days. The obtained polymer was washed repeatedly with acetone to obtain a brownish acicular polymer. When the Raman spectrum of the polymer was measured, there was no C=C peak near 1600C1i, and the IR spectrum was also based on C=C (no absorption,
The other absorptions were almost the same as those before the 250"C heat treatment.

I R (KBr) 2963cm-', 1721cm-
'+1610cm-'.

1306CI-'+ 1216CIIl-'l 111
2CI11-' When observed with a stereoscopic microscope and a polarizing microscope, the polymers obtained by the present invention in Examples 1 to 4 above were found to be different from polymers in which only diacetylene groups were reacted (relatively, double bonds were reacted). It is thought that the crystal structure did not change much after that.

Claims (1)

[Claims] The structural formula of the monomer is R^1-X-R^2-C≡CC≡C-R^3-X-R^
4 (Here, R^1, R^4 are monovalent organic groups, R^
At least one of 1 or R^4 contains a double bond, and
is an ester group or an amide group, and R^2 and R^3 are divalent organic groups. ) A polydiacetylene obtained by prepolymerizing the diacetylene group of a double bond-containing diacetylene compound and then reacting the double bond part.