JPS5951904A - Polyacetylene film and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel film polyacetylenes having several desirable properties, such as elongation at break, tensile strength, and molecular orientation upon stretching.

Furthermore, the present invention also relates to a method for producing the polyacetylene film.

Conventionally, compounds of transition metals and periodic table 1A,
It is known when acetylene polymers are prepared by polymerizing monomers in the presence of a catalyst composition consisting of organometallic compounds of elements of groups 2A, 3A and 4A. Similarly, it is well known that a film-like acetylene polymer can be directly obtained by such a polymerization reaction. However, none of the conventional methods has been able to produce acetylene polymers that have the desired number of properties in terms of elongation at break, tensile strength, and molecular orientation upon stretching, or that can be formed into films.

According to conventional methods, acetylene polymers are produced in various forms. For example, in powder form (G.

NATTA et al. [REND, ACC, NAZ, LI
NCEI J 5CIENZE.

NAT, NAT, , 2'5, 3 (195B)
(See Reference A). This document discloses the use of a catalyst consisting of titanium alcoholade and trialkylaluminium.

This yields a crystalline, powdery polymer, but when formed into a film it is brittle and has no mechanical resistance.

It is in the form of a flexible film (4'! Gansho 48-32581
No. (Reference B), Japanese Patent Application No. 142012 (Reference C)
, European Patent Application No. 26234 (March 2, 1980)
8th) (see Reference D)). The film thus obtained is stretched with a stretching ratio of 2 to 2.8, operating at room temperature. However, the molecular orientation is small.

It is a bulky or partially gelled polymer (U.S. Pat.
, 228, No. 060 (Reference E)). These polymers have the same drawbacks as those of Reference A and are not stretch oriented. Furthermore, the catalysts used to polymerize the monomers are of a special type and are expensive.

It is a gel-type substance (Yorotsu Patent Application No. 26)
No. 235 (March 28, 1980) (Reference G)).

In this case, the film obtained by compressing the polymer is not stretched and is therefore non-oriented.

It is a film obtained by polymerizing acetylene under shear flow conditions (Synthetic Metals "5").
ynthetic Metals J 4, 81 (
1981) (see Reference H)). The properties of the films obtained by this method are not satisfactory, and furthermore, their relative electron diffraction spectra show a negligible preferential orientation upon stretching.

The inventors have discovered that acetylene can be polymerized in the form of a film with the potential to overcome the drawbacks of conventional methods and to obtain high levels at breakage (similar to those obtained for fibers), and the present invention provides It's arrived.

It is an object of the present invention to provide a new polyacetylene film that has a number of desirable properties not found in conventional acetylene polymers.

Another object of the present invention is to provide a method for producing such a polyacetylene film.

Other objects of the invention will become apparent from the description below.

More specifically, according to the method of the present invention, the temperature -10
At 0 to +100°C1 acetylene pressure of 0.01 to 2 atm, the acetylene monomer is heated according to the general formula % [where X is -NRIR2 and -8R3 (here R1
1R2 and R3 are hydrocarbon groups having 1 to 20 carbon atoms,
A cycloalkyl group having 4 to 6 carbon atoms or an aromatic group -0-C6H4-CH3' (
cresyl group), -0-C,H40--]: or -0OC
-R5 (where R4 and R5 are R1, R2 and R3
and m is an integer of 1 to 4] and 2) a group selected from the group consisting of Contacting with a catalyst composition which is an alkyl derivative (wherein the alkyl group has 1 to 20 carbon atoms) and in which the molar ratio of component 2) to component l) is from 1=1 to 10:1. Yes, the thickness is about 5 microns to about 1
Acetylene can be polymerized as a +nm film.

Representative components of component 1) of the catalyst composition which can be used particularly advantageously are as follows.

Ti (N(n-C31b)2)4 Ti (N(n-C3H7)z)2 ((o
n Cd(9h)T'i (N(+1-C5Ih)
2 ) 2 ((C113COO) 2 )
'I”j (N(n C3H7)2)2 (
(0-C6H4CH3)2)Ti(N(C113COO
)2) ((OC6H4CH3)2)Ti ((
0-C6H4-C[(3) 2) ((0-1
1-C4H9) 2)1'! (N(II C3+
-17)2 )2 ((S-C61-1sh)
'r1((o-c,,R4-o)) ((o-
n-c4r=+9)z) Component 2) of the catalyst composition includes sodium alkyl, lithium alkyl, potassium alkyl, potassium alkyl, sodium alkyl, alkylmagnesium halide, alkylzinc, a)
Ruboron, alkyl aluminum, alkyl gallium,
Alkyltin and alkyl chains can be used). Among these, trialkyl aluminum oxides are preferred.

The catalyst composition is prepared by contacting components 1) and 2) in the above proportions in an anhydrous and inert organic solvent (non-reactive solvent) such as hexanoyl, butalohexane and toluene. A solution is obtained by maintaining the temperature at 20 DEG to 100 DEG C. for 0.5 to 15 hours.

The catalyst solution thus obtained is sprinkled onto the surface of the solid, the solvent is then removed by evaporation under reduced pressure, and acetylene is then fed to the dispersed catalyst to form a film of heavy metal. Induces coalescent growth.

The optimum temperature for polymerization is in the range -80 to +20°C. This range produces an acetylene polymer with an isomer content of about 40% or more.

It is known that the amount of ance and trans isomers contained in a polymer depends on the polymerization temperature ([Journal of Polymer Science (J. Po
lym. Sci. ), Pol. Chetn.
I(cl..

12, 11 (1974) (Reference I)).

As mentioned above, the polymerization reaction is carried out under a pressure of 0.01 to 2 atmospheres of acetylene. Pressures higher than the above upper limits can be employed, but in this case special attention must be paid to the pressures in view of the instability of acetylene.

The catalyst composition of the present invention is an essential factor in order to obtain a polyacetylene film with desired properties. In fact, when using a titane alcoholate represented by the general formula Ti(01%)4 [known as a component of a catalyst composition in the polymerization of acetylene (see Reference A)], orientation by stretching is particularly important. As far as degree is concerned,
- It must be taken into account that a strong polymer is produced.

By operating according to the method of the invention, an acetylene polymer film is obtained which in principle has the following properties:

Contains cis-isomers Approximately 40% thick
5 microns or 1 pharynx M/-? jll
elongation (IVIJ o ) of 4.00% tensile strength greater than 4.00% orientation by stretching from 100 MPa As will be described later, X-ray scattering angle (
Δβ) 35° or less” As mentioned above, these characteristics were completely absent in polyacetylene films produced by conventional methods.

Regarding the last property, this property was confirmed by X-ray diffraction tests. The X-ray diffraction spectra of isotropic crystalline or semicrystalline materials are characterized by reflections that appear in the form of continuous circles.

If instead there is a phenomenon of preferential orientation of the crystalline fraction, the reflections tend to appear as arcs of circles or, under limited conditions, as points if the phenomenon of preferential orientation is particularly strong. Scattering of the intensity of the semi-reflection along the circumference of the circle (usually azimuthal 5c
(referred to as atter) is used as an index of the preferred orientation of the material.

X-ray diffraction spectrum of stretched polyacetylene (
(described later) was obtained using CuK (λ=1..5418 A) line α in a flat Goo Yamba. All of the samples tested exhibited a preferred orientation of crystals of the monodimensional type, with the crystal axis C parallel to the stretching direction (coinciding with the axis of the macromolecule).

The above conclusion is based on the literature (Reference L: “Journal of Polymer Sci.
) J Polym.

Lett, +ga. 20, 97 (1982))
This is based on data on the properties of the structure described in "2.

For the index of the degree of preferred orientation, on the diffraction pattern itself, it corresponds to the strongest reflection present for the distribution of the pattern at 2θ = 23° to 24° (according to the reference grating planes 110 and 200). Total azimuthal scattering of the arc (Δβ(
0), see Figure 1). The minimum value of Δβ clearly corresponds to the maximum degree of preferred orientation.

In materials such as drawn fibers and rubber (characterized by a high level of preferred orientation), Δβ exhibits values of approximately 20° (Reference M: "Makromol/Kule Gummy"). .

Chem, ) J 181. 1143 (1980)
).

For the sake of simplicity, substances with values of 25° to 35°, 35° to 50', and 50° with a Δβ value of 25°''! are classified as materials of type I, U, mark, and ■, respectively. (See Figure 1). Examination of the X-ray diffraction spectrum based on the above description and with reference to the experimental examples shows that the polyacetylene film of the present invention has extremely high preferential orientation upon stretching. 2nd A
Figures 1 and 2B are representative examples.

Figure 2A l/lo = 4-5 Figure 2B l/1O-6,5 Each sample was measured using a dynamometer In5tron Model 1
121 (operated at room temperature), both in air and in a nitrogen atmosphere, with a stretching rate ε=25 minutes.

The stretching and molecular orientation properties of samples obtained by conventional techniques are described in the literature (Reference C1 Reference N: [J
, Polymer Sci, J. Polymer
r Lett, Ed, 17, 195 (1979)
and Reference 0: “J, Polymer, Sci
, J., Polym.

Phys, Ed., 18, 429 (1980)).

All of these references report that the maximum straightness of the draw ratio l/llo is about 3.0, and only modest values of molecular orientation are disclosed.

The inventors prepared a sunglass according to the disclosure of reference C and according to the disclosed method, the stretch ratio was 1./I.

-, the sample was stretched at a knee of 2.5. The X-ray diffraction spectrum of the thus stretched material is shown in FIG.

In this case as well, the sample was stretched at room temperature, but the operation was performed in a nitrogen atmosphere. Comparing Figures 2A, 2B, and 3, it is clear that there are significant differences in molecular orientation. moreover,
It is clear that the molecular orientation of the materials prepared according to the disclosures of References B, C and D is quite far from that obtained for general to fibers.

Films prepared according to the invention have improved mechanical properties as evidenced by the fact that the tensile strength is more than 100 MPa higher than that for the reference N film, which is approximately 20 M1)a. There is also a clear difference.

Another significant difference between the films of the present invention and those of the prior art is seen in the behavior of the films towards oxygen.

According to reference N, the draw ratio is very sensitive to oxygen and clearly decreases after 1 minute of exposure to air.

Even when the film obtained according to the present invention was stretched after being exposed to air for a period of not less than 15 minutes, there was almost no difference between the film and the conventional sample stretched under a nitrogen atmosphere. .

The high degree of orientation due to the stretching of the film according to the invention gives this film the important property of optical anisotropy, which is related to the polarization of the light transmitted through the thin layer. Such polarization can be revealed by optical microscopy of the sample with light polarized through a Nicol prism.

The extinction phenomenon is detected when the fibril direction of the stretched sample is perpendicular to the direction of the Nicol plane of polarization. Complete extinction (detected by Kokichi, where the field of view of the microscope becomes dark) indicates that the molecular orientation phenomenon involves all of the fibrils in the complete sample.

Besides optical anisotropy, the stretched film according to the invention also has electrical anisotropy. This anisotropy is confirmed by the fact that the conductivity of the material in the direction parallel to the drawing plane is greater than in the perpendicular direction.

Due to the high anisotropy found in the stretched film according to the present invention,
This film has important applications in the field of optics, in the preparation of electrical devices such as homo- or heterojunctions, electrodes for positive electrode redundancy reactions, photovoltaic cells, and in the manufacture of electrodes for dry cells and accumulators.

Next, a general method for preparing a catalyst composition and polymerizing acetylene in the presence of the catalyst composition will be described. All operations are carried out by the techniques normally employed for this purpose, using solvents which have been rigorously freed of both oxygen and moisture and which have been previously dehydrated and degassed.

Preparation of Catalyst Composition A three-necked flask equipped with a reflux condenser and maintained in a nitrogen atmosphere is sequentially filled with hexane (solvent), a titanium compound, and an amount such that the alkyl aluminum atomic ratio is 4/'1.

This gives a solution which is maintained at the boiling point temperature of the solvent under atmospheric pressure for 10 hours.

The mixture is then cooled to room temperature 1 and the catalyst solution thus obtained is used for the subsequent polymerization of acetylene.

Polymerization of Acetylene The polymerization of acetylene is carried out in a large test tube (the black one shown in FIG. 4). The test tube is placed in a horizontal position. A certain amount of catalyst solution (prepared as in #Ji) containing 1 mg atom of titanium (mpA) is charged into it. This test tube is connected to a vacuum pump via a glass cone C. Then, gradually release the cock R and rotate the test tube. Slowly evaporate the hexane in the catalyst solution. As a result, a liquid and viscous layer (S) adheres to the wall soil 11 of the test tube.

When the solvent has been completely distilled off, the layer adhering to the walls will no longer flow, even when the test tube is held vertically.

At this stage, cock R is closed and the acetylene is heated to a constant pressure of 600 mrn Hg in a thermostatically controlled bath at the desired temperature.
Connect to equipment maintained in A gas is brought into contact with the catalyst layer through a cockpit to polymerize, producing a film-like polymer on the surface of the catalyst.

A second catalytic layer is formed on the polyacetylene film 11 adhering to the test tube wall, operating in the same manner as employed to form the first layer. In this way,
Polymerization is repeated several times until a film of the expected thickness is obtained.

Once the desired amount of acetylene has been absorbed, the polymerization is stopped by removing the remaining gas and the polymer film adhering to the test tube wall is removed.

The resulting film is washed by thorough immersion in an aliphatic or aromatic organic solvent (eg, hexano, toluene, etc.) at the same temperature at which the polymerization was carried out.

This transfers the catalyst to the liquid phase, from where it can be recovered and reused. The washing step continues until the solvent is colorless.

Thereafter, the polymer is dried under reduced pressure using a pump, and a uniform film is recovered. The film exhibits a specific metallic luster.

Referring to Table 1 below, Examples 1 to 6 relate to the polymerization of acetylene using a catalyst according to the invention and carried out according to the method described above.

Examples 7 and 8 are comparative examples; Example 7 was carried out according to Example 1 of Reference C, and Example 8 was carried out according to Reference O.

From the films obtained according to Examples 1 to 8, small pieces of 0.5 x 5 cm were cut out in a nitrogen atmosphere. A mutual comparison was made based on Δβ. The results obtained are shown in Table 2.

The film obtained according to the invention has a very high specific conductivity when doped with iodine.

The value of this specific conductivity reaches its highest value when the polyacetylene film is pre-stretched with a stretching ratio of 6 or higher.

More specifically, an iodine-doped stretched polyacetylene film has an intrinsic conductivity along the stretch direction that is an order of magnitude higher than that of a similar unstretched film doped with the same amount of doping agent. have.

Furthermore, doped polyacetylene films according to the invention exhibit unexpectedly high specific conductivities compared to polyacetylene films prepared by conventional methods, even though doped with the same amount of doping agent.

Corresponding to these results, according to one embodiment of the invention, the polyacetylene film is doped after having previously been stretched with a stretching ratio of 6 or more, or without stretching.

Doping with iodine was carried out to achieve the maximum content of iodine (17 mol %) in the film, thereby producing a doped and optionally hand-stretched polyacetylene film with a maximum intrinsic conductivity of 2000 Ω cm. is obtained.

The stretching ratio is expressed by the following formula.

Here, lo is the initial length of the polyacetylene film and l is the length of the same film after stretching.

According to one embodiment, a polyacetylene film, optionally stretched at a stretch ratio of about 6 or more, can be isomerized to convert it to a trans-dominant type prior to doping with iodine.

Typically, isomerization is carried out by maintaining the film in a helium stream at a temperature of about 200° C. for several minutes (e.g.
(minutes).

Polyacetylene films thus isomerized and optionally stretched have, after doping with iodine, an intrinsic conductivity (σ) of approximately −1−1 2000 Ωcnt.

Doping is carried out by contacting an optionally stretched and isomerized polyethylene film with iodine vapor at a temperature of -10'C to 50'C. According to another embodiment, this is also carried out by contacting the optionally stretched and isomerized film with a solution of iodine in a hydrocarbon (eg pentane). In this case as well, the operation is carried out within the above temperature range. In either case,
The time of contact is monitored so that the iodine content in the film is 7 mol.

Example 9 Hexane (solvent), Ti ((cresyl) 2
) ((On -C4H9)2) and AJ! '(
Filled with C21(5)3 (atomic ratio of Al/Ti = 4/1).

A solution was obtained which was maintained at the boiling temperature of the solvent under atmospheric pressure for 10 hours. The mixture was then cooled to room temperature.

A large horizontally oriented test tube was filled with a certain amount of the catalyst solution containing 2 m9 of titanium prepared as described above. This test tube was connected to a vacuum source, and while rotating, the solvent hexane was slowly distilled off, and a liquid and viscous layer of catalyst was deposited on the inner wall of the test tube. The test tube was then placed vertically in a thermostatically controlled bath at -40"C and connected to a device containing gaseous acetylene at a constant pressure of 600 mm Hg. It was polymerized as a film of thickness o, i mm on the inner wall.

The film was cleaned by immersing it in hexane and treating it at polymerization temperature to dissolve the catalyst pigeons.

Washing continued until the solvent was colorless. At this stage, the polyacetylene film was dried under reduced pressure and recovered.

In this way, a specific metallic luster and approximately 400c
A film with a specific area of rl was obtained.

Cut a 3 x 6 cm piece of tape from this film.
In5tron Mod, 1121, stretching ratio ε=25
It was stretched for 1 minute.

The tape had the following properties:

Cis unit content: 75% Trans unit content: 25 elongation at fracture (l
/lo) 7.5 tensile strength
140 MPa (In the example, a polyacetylene film prepared by the method described above was doped. More specifically, doping in the gas phase is carried out in a glass apparatus connected to a vacuum pump and connected to a container containing the iodine vapor and another container containing the polyacetylene film prepared as described above. ,Ta.

Example 10 A sheet cut from polyacetylene prepared according to Example 9,
The tape stretched in an In5tron at a stretching ratio α=7.5 was isomerized at 200° C. for 5 minutes in a helium stream. This resulted in a polyacetylene with a trans unit content of 95 units, which was further treated with iodine vapor as described above to give an adsorption amount of 15 moles.

The tape doped in this way had an intrinsic conductivity in the stretching direction σ = 2000 Ω cm.

Example 11 The same treatment as in Example 10 was carried out, but the isomerization step was omitted. By doping with iodine, a polyacetylene with 13 moles of iodine was obtained, which had a specific conductivity in the stretching direction σ = 1800 Ωcrtt.

Example 12 A polyacetylene tip prepared according to Example 9 was isomerized according to the method of Example 10 without slow stretching and doped to 15 moles of iodine. For samples doped in this way, the intrinsic conductivity σ is 1
It was 60Ωcm.

Example 13 A polyacetylene tape prepared according to Example 9, without stretching, was doped with iodine in an amount giving an adsorption of 15 mol. The sample doped in this way had an intrinsic conductivity of 1600 cm.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an X-ray diffraction pattern for determining the degree of preferential orientation of the polyacetylene according to the present invention and the classification of substances according to the scattering angle. J'L, Figure 3 shows an X-ray diffraction spectrum for a polyacetylene film produced using a conventional method.
and FIG. 4 are diagrams showing one specific example of an apparatus that can be used to produce a polyacetylene film according to the present invention. Purification of the drawing 1μ (content changed garden △ / 75 Nobu Tsu H Nao (0)
Appeasement Poyance・13 Know Qift 0<2
51 25-35
1+35-50
11+>50
1V Extension-) Written amendment to old proceedings (method) September 8, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1, Patent Application for Indication of Case 141247 1982
No. 2, Title of the invention Polyacetylene film and its manufacturing method 3, Person making the amendment Relationship to the case Applicant. 5. Date of amendment order Showa year, month, day 6. Subject of amendment (1) Application for correction
1 copy (2) Engravement of the detailed statement (no change in content) 1 copy (3
) Engraving of drawings (no changes in content) 1 copy 7, details of amendments as attached.

Claims (1)

[Claims] 1. Thickness = 5 microns to 1 intestine, cis isomer content = 4
0% or higher, elongation at break C1l/l)o) = 4 or higher, tensile strength: 100 MPa or higher, molecular orientation due to stretching = X-ray scattering angle ° (Δβ) 35° or less A polyacetylene film characterized by having the following properties. 2. Thickness = 5 microns to 1 porcelain, cis isomer content = 4
0% or higher, elongation at break (l/lJo): 4 or higher, tensile strength: 100 MPa or higher, molecular orientation by stretching: X-ray scattering angle (Δβ) of 35° or less. In the method for producing a polyacetylene film having a temperature of -1
00° C. to +100° C. and an acetylene pressure of 0.01 atm to 2 atm.
゜R2 and R3 are hydrocarbon groups having 1 to 20 carbon atoms,
Cycloalkyl having 4 to 6 carbon atoms or aromatic group having a methyl substituent in the ortho, meta or para position with respect to the carbon bonded to oxygen, Y is 1OR4 and 100C R
s (where R4 and R5 are R1, R2 and R3
A group selected from the group consisting of 1, m is an integer from 1 to 4] and 2) an alkyl group of an element in groups 1A, 2A, 3A and 4A of the periodic table, where the alkyl group has 1 to 20 carbon atoms. )
The molar ratio of component 2) to component 1) is 1:
A method for producing a polyacetylene film, characterized in that acetylene is polymerized in film form by contacting with a catalyst composition having a ratio of 1 to 10:1. 3. Component 1) of the catalyst composition is Ti (N(n-C3H7)2)4'r! (N(n C3H7)2)2 ((0-
n C4H9)2) Ti (N (n-C3H7) 2
) 2 ((CH3COO) 2 )Ti(N
(n C3H7)2)2 ((0-C6H4-C
H3)2)T! (N(C+7Hs3COOh) (
(0-C6H4-CH3)2')'ri ((0-C6
H4CH3)2) ((0-n-C4H9)2)Ti
(N(n-C3H7) 2)2 ((S-C6
H5)2)TI((0-C6H40))((0
-n C4H9')2)4, component 2) of the catalyst composition is sodium argyl, lithium argyl, potassium alkyl, beryllium alkyl, beryllium alkyl, alkylmagnesium halide, zinc alkyl, boron alkyl, aluminum alkyl, alkyl gallium,
The method according to claim 2, wherein the method is selected from the group consisting of alkyltin and alkyl chains. 5. The method according to claim 4, wherein component 2) of the catalyst composition is trialkylaluminum having an alkyl group having 1 to 8 carbon atoms. 6. The method according to claim 2, wherein components 1) and 2) of the catalyst composition are brought into contact with an anhydrous and inert solvent (non-reactive solvent) at a temperature of 20°C to 1 to 100°C. 7. The method according to claim 6, wherein the inert solvent is selected from the group consisting of hexane, chlorohegisan and toluene. 8. The manufacturing method according to claim 2, wherein the polymerization temperature is between 180°C and 20°C.