JPS5832608A - Preparation of 2-alkynes and their preparations - Google Patents

Abstract

PURPOSE:To obtain the titled soluble and high-molecular weight polymer in high yield applicable as a semiconductor, gas absorber, separating film, photoresist, etc., by polymerizing a 2-alkyne in the presence of a catalyst of the MoCl5- or WCl6-reducing agent type. CONSTITUTION:A 2-alkyne (e.g., 2-hexyne, etc.) shown by the formula[R is (substituted) alkyl except methyl]is polymerized in the presence of a catalyst obtained by combining MoCl5 or WCl6 as a main catalyst with a reducing agent (e.g., tetra-n-butyltin, triphenyl-antimony, etc.) such as an organometallic compound, metal hydroxide, etc., to give a chain polymer having a molecular weight >=10,000. A ratio of the 2-alkyne to the catalyst is properly 100:(5-0.2) by weight and a molar ratio of the reducing agent to the main catalyst is 0.3-3. A (halogenated) hydrocarbon, etc. is preferably used as a solvent for polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polymer and a method for producing foam, and the first object of the present invention is to produce a novel polymer containing 2-alkynes as a monomer. Our mission is to provide
The first object of the present invention is to provide a method for producing such a polymer at a high reaction rate. According to the present invention, the above first object is achieved by the general formula % formula % (1) (In this 2, R is an alkyl group other than a methyl group, and this alkyl group has 7 or more hydrogen atoms as substituents. According to the present invention, the second object is achieved by a chain polymer having a molecular weight of 10,000 or more and having a co-alkyne monomer represented by
This is achieved by polymerizing a λ-alkyne represented by the formula in the presence of a catalyst comprising molybdenum pentachloride or tungsten hexachloride in combination with a reducing agent.

Conventionally, Ziegler-type catalysts (e.g., titanium tetra-n-butoxide or a mixture of iron acetylacetonate and organoaluminum compounds) have been very difficult to polymerize unsubstituted acetylenes and terminal acetylenes such as /-hexene and phenylacetylene. It became an effective catalyst, and a high molecular weight polymer was obtained in high yield. However, internal acetylenes such as λ-alkynes were not substantially polymerized by Ziegler catalysts due to steric hindrance, and high molecular weight polymers were not obtained. proposed a method for producing polymers from acetylene derivatives using a catalyst (Tokuko Sho!j-23j6j,
J-/7θy2 No. 3037, Sho J3-307.22, Sho J J-106 GJ6)'.

The present inventors further conducted extensive research on polymerization methods for obtaining high polymers from internal acetylene, and found that co-alkynes can be polymerized by using a catalyst consisting of a combination of molybdenum pentachloride or tungsten hexachloride and a reducing agent. proceeds easily, the resulting polymer is soluble, and its molecular weight is very large (molecular weight of 70,000 or more, especially /θ0,000 to /θθ-10,000).
The present invention was completed based on this finding.

The present invention will be explained in detail below.

In the co-alkynes of the present invention represented by the general formula CH, -0miC-R, R is an alkyl group other than a methyl group, and this alkyl group may further have a substituent,
Examples of the substituent include an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, and a halogen.

The polymerization catalyst in the present invention is molybdenum pentachloride (MOO
4) Or, tungsten hexachloride (WC41) is used as the main catalyst, and various reducing agents are combined with this as the second component.

Various organometallic compounds and metal hydrides are used as the reducing agent. Examples of organometallic compounds include those containing boron, aluminum, silicon, tin, lead, arsenic, antimony, and the like.

Among these, organic tin compounds such as tetraphenyltin and tetra-n-butyltin are particularly preferred in terms of ease of handling, availability, and effectiveness. Further, as the metal hydride, lithium aluminum hydride, sodium borohydride, sodium hydride, etc. are used.

The weight ratio of the 2-alkynes, which are monomers, and the main catalyst is appropriately within the range of 3 to O0 for the former, and the ratio of the reducing agent to the main catalyst is 0 in terms of molar ratio. A range of .3 to 3 is preferred. The catalyst is preferably used in the form of a solution, and the main catalyst and reducing agent are dissolved in a solvent (the same solvent as the polymerization reaction solvent described later is used), and the solution is left at 30 to 60°C for 10 to 60 minutes before use.

As the solvent for the polymerization reaction, it is preferable to use hydrocarbons, halogenated hydrocarbons, and the like. In particular, hydrocarbons such as benzene, toluene, and cyclohexane are easily available,
It is also preferred because a high yield can be achieved in polymerization.

The monomer concentration in the polymerization reaction is preferably in the range θ, / to j moles/l. The temperature of the polymerization reaction is usually selected from θ to 60°C, and the reaction time is selected from the range of several tens of minutes to several tens of hours.

After the reaction is completed, the reaction system is diluted with the solvent used in the reaction and then poured into a large amount of methanol, which precipitates the produced polymer, which is then separated in an oven and dried.

According to the present invention, novel chain polymers can be obtained in high yield from λ-alkynes.

The produced polymer is 70,000 or more, especially 100,000 to /θ00,000,
As an acetylene polymer, it has an extremely high molecular weight and is characterized by being completely soluble in hydrocarbons such as toluene and cyclohexane. The polymer thus obtained can be applied to semiconductors, gas adsorbents, separation membranes, photoresists, etc.

Next, the present invention will be explained in more detail with reference to Examples.

Example/ 30 mmol of molybdenum pentachloride and 30 mmol of tetraphenyltin were added to toluene/1c13 that had been sufficiently purified under a dry nitrogen atmosphere, and the mixture was aged at 30° C. for about 11 minutes.

Add i,o mol of 2-hexine to the obtained catalyst solution to give %
Polymerization was carried out at 30°C for 2 hours.

After the reaction is complete, mix! After dissolving in t of toluene,
Pour into a large amount of methanol to precipitate the produced polymer,
Dry in oven. Is the amount of methanol-insoluble polymer produced relative to the amount of cohexin charged? It was λ%.

According to the light scattering method, the weight average molecular weight of the produced polymer is /10
Intrinsic viscosity/d measured in toluene at 30°C
Y, j j di/f.

The resulting polymer is a white solid, containing benzene, toluene,
Cyclohexane, n-hexane, tetrahydrofuran'
It was completely soluble in carbon tetrachloride, chloroform, and diethyl ether, and insoluble in ethylene dichloride, acetone, ethyl acetate, nitrobenzene, and acetonitrile.

The analytical values of the produced polymer are as follows.

As elemental analysis value C(C11H1o)n]; calculated value,
C,? 7.73%; H, /2.27% actual value, O, c
! '7. Geta%; H2/co1.27% Infrared absorption spectrum: 3000-21? ! 0(e), /ljθ~/jrθ
(W), /4t7θ(B).

/32θ(m), /26θ(b), ///θ~/θθ
O Tsukuda).

FOO(@, ?2θ(m) cm-'.

Ultraviolet absorption spectrum; (cyclohexane) λmax 290 nm, g ma
x/2θθnm, absorption limit 3jθnm.

Carbon/3 nuclear magnetic resonance spectrum (I-substituted chloroform) δ/3f, 0 (C3), /32,3 (C2), 34
．． θ(0,).

201. f(C,), /ri, ♂(c,), i's,
o (C1l) ppm From the analysis results of c+ or higher, it is concluded that the resulting polymer has the expected structure shown below.

(n is 13,000 on weight average) The softening point of the produced polymer was 222 to 237°C, and according to differential thermal analysis, only heat generation was observed near the softening point. Even when this polymer was left in the air at room temperature for several months, the molecular weight hardly decreased.

Example 2 Cohexine was polymerized in the same manner as in Example except that tungsten hexachloride was used as the main catalyst instead of molybdenum pentachloride. The amount of methanol-insoluble polymer produced was 57% of the amount of monomer charged. The weight average molecular weight of the produced polymer was 200,000, and the intrinsic viscosity at 30°C in toluene was 0. ! It was a di/ri.

Comparative Example: A reaction was carried out in the same manner as in Example/, except that the main catalyst, molybdenum pentachloride or tungsten hexachloride, was used alone without using a reducing agent. The yield of coalescence was 0%.

Example 3 Molybdenum pentachloride was used as the main catalyst, and as the reducing agent,
Cohexin was polymerized in the same manner as in Example 1 using the compounds shown in the table below. The yield and intrinsic viscosity (in toluene, 3θ°C) of the produced polymer are shown in the following table.

Reducing agent Yield (%) Intrinsic viscosity (di/l) Molecular weight Tetra-n-butyltin 〈/3. Da 6 gu? 10,000 triphenyltin chloride! 3 3.3
/ 4.12 million tribenzyltin chloride <
17 6.6/ 2! tO million triphenyl antimony 4t3 4t, lθ
Example 700,000 The reaction was carried out in the same manner as in Example 7, except that ethylene dichloride was used instead of toluene as the solvent, and the amount of polymer produced was proportional to the amount of monomer charged. λ%,
The intrinsic viscosity of the polymer was j, / / dA' / f (molecular weight approximately 350,000).

Example! Polymerization was carried out at 60°C in the same manner as in Example/, and the amount of polymer produced was 1% of the amount of monomer charged.
Is the intrinsic viscosity of the polymer 2.20 dll? (molecular weight approximately 30,000) Example 6 As a monomer, 0. Polymerization was carried out in the same manner as in Example except that 0 mol of 1-heptine was used to obtain a chain polymer of --heptine. The yield of the produced polymer was 57%, and the intrinsic viscosity (in toluene, 30°C) was j, j Odi/f
(molecular weight approximately! θ million). The solubility of the resulting polymer in various solvents was similar to that of poly(cohexine).

The infrared absorption spectrum and ultraviolet absorption spectrum of this product were as follows.

Infrared absorption spectrum; 3θθ0~2rjO(e), /4jO~/rjO(
v? ).

/4t70(s), /J70(m), N2
70 @), /200 (v/).

/10θ), 100θ(w) + 720(W)
s Ultraviolet absorption spectrum (in cyclohexane); λ On
Shoulder (ε?/θ) at m Absorption limit, ? j Onm Example 2 Polymerization was carried out in the same manner as in Example 1 except that 0.50 mol of co-octyne was used as the monomer to obtain a -1-octyne chain polymer. The yield of the produced polymer was 63%, and the intrinsic viscosity (in toluene, jθ'c) was J,/4a/f (molecular weight approximately J/10,000). The solubility of the resulting polymer in various solvents was similar to that of poly(2-hexyne).

The analytical values of the produced polymer were as follows.

Elemental analysis value [as (C11H14)H]; calculated value, O
, J"?, /9; H, /, 2. J'/.

Actual value, O, J'4j7; H, /2. ri l.

Infrared absorption spectrum; 3θ00~ko♂! θ(θ), /660~isro(w)
.

/4t70(8), /370(m), /,24
(7(W), /100(p).

1010fp), IO'0@), ? 2θ (m)
.

Example 1 Polymerization was carried out in the same manner as in Example 1 except that O, -tO mol of cornonine was used as the monomer, to obtain a chain polymer of λ-nonine. The yield of the produced polymer was 60%, and the intrinsic viscosity (in toluene, 30°C) was -20 dll? (molecular weight approximately 270,000).

The solubility of the resulting polymer in various solvents was similar to that of poly(--hexyne).

Further, the infrared absorption spectrum and ultraviolet absorption spectrum of this product were as follows.

Infrared absorption spectrum; 3000-8jO (day), /660-1st
rθ0ri.

/4t7θ~/4tjO(8), /370~/36
0←).

/llθ(→, /θ7θ(w), 10101o(,
7Jθ←) Ultraviolet absorption spectrum; Shoulder (εrizO) absorption limit j4 at 2/Onm
tjnm Example Polymerization was carried out in the same manner as in Example 1 except that 0.10 mol of copesin was used as a monomer to obtain a chain polymer of copesin. What is the yield of the produced polymer? θ%, and the intrinsic viscosity was λ, 3/di/f (molecular weight approximately -!0,000). The solubility of the resulting polymer in various solvents was similar to that of poly(2-hexyne).

The analytical values of the produced polymer were as follows.

Elemental analysis value [as CCl0H18)n]; calculated value, O
, rt, J”r; H, /3./2 actual value, 0.7
6, j/ ; H, /2. Infrared absorption spectrum: 3000-2rjθ(s), 1tjo~/j♂θ(
W).

/7θ(s), /37θ(m), /J40(
W), /10θ(m).

/θ3o ~lo10(m), troo(W),
72θ (m) ultraviolet absorption spectrum; shoulder (εjθθ) absorption limit 33jnrn Example IO Tetra-'n- instead of tetraphenyltin as a reducing agent
Using butyltin, 0.0% co-alkyne as shown in the table below. j
Polymerization was carried out in the same manner as in Example except that 0 mol was used, and the results shown in the table below were obtained.

--Heptin 2! Ko, 4t4. 27
By any chance Octin! 2 ko, 20 λdaman 2-nonin 67 8? Oλθ Should happen - Desing 2 2.10 2j 10,000 Above example/1j, 6
,? The polymers obtained in , 11 and IO were made into toluene solutions and cast to obtain transparent and durable films. The polymer films became more flexible in the order of λ-hexyne, -monohebutyne, -monooctyne, λ-nonine, and λ-decyne.

What has been explained above and shown in the examples are representative examples to help understand the present invention, and the present invention is not limited to these examples, and may include other examples within the gist of the invention. It is possible to take a modified example.

□ Applicant Toshinobu Higashimura Agent
Patent law civil engineering color Hayashi

Claims (2)

[Claims] (1) General formula % Formula % (In this 2, R is an a=l group excluding a methyl group, and one or more hydrogens of the alkyl group may be substituted with a substituent.) A chain polymer with a molecular weight of 10,000 or more, whose monomer is 2-alkyne represented by (2) General formula % Formula % (In this formula, R is an alkyl group other than a methyl group, and this alkyl group may have one or more hydrogen atoms substituted with a substituent.) A method for polymerizing non-alkynes, which comprises polymerizing λ-alkynes in the presence of a catalyst comprising a combination of molybdenum pentachloride or tungsten hexachloride and a reducing agent.