JPS5825688B2 - Cycloolefin Injiyugoutaino Seizouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an industrially advantageous method for polymerizing cycloolefins, and is characterized by a reaction obtained by reacting a tungsten salt with a Lewis acid and molecular oxygen. The purpose of this invention is to use a novel polymerization catalyst system in which a product is used as a base and organometallic compounds from Groups 1 to 2 of the periodic table are combined therewith.

Regarding the polymerization of cycloolefins, it has already been known by Natsuta et al. to use a catalyst system consisting of a salt of a transition metal of Group I or VIB and an organometallic compound (Angew, Chem, 76, 765).

However, since a very large amount of catalyst is required for seven polymers and the polymerization activity is low, the cost of the catalyst is a very big obstacle from an industrial standpoint.

Therefore, it is already known that there are attempts to increase the activity and reduce the amount of catalyst by adding various activators to these catalyst systems as a third component.
No. 26631 describes a catalyst system comprising tungsten hexachloride and an oxygen-containing compound as activators in combination with an organometallic compound.

However, even with the addition of such an activator, an extremely highly active catalyst system cannot be obtained, and the catalyst efficiency remains unsatisfactory, and the fundamental problem of reducing catalyst cost cannot be solved yet. (See comparative example)
.

Therefore, in producing cycloolefin polymers which are extremely interesting and useful in terms of physical properties, the problem of reducing catalyst costs has become an extremely important industrial issue.

In view of this point, the present inventors have finally arrived at the present invention as a result of intensive research, and the characteristics of the present invention are that it is impossible to polymerize conventional cycloolefins. The present invention has surprisingly high activity and can obtain the desired polymer in high yield with an extremely small amount of catalyst.According to the present invention, it is possible to reduce catalyst costs in the production of cycloolefin polymers. This method can sufficiently solve a very important problem, and in addition, it is extremely advantageous in terms of polymer production in that it does not require a special catalyst removal step.

In the present invention, a cycloolefin, which is a cyclic hydrocarbon compound having 4 to 5 carbon atoms and 7 or more carbon atoms and has at least one carbon-carbon double bond in the ring, is prepared using a tungsten salt, a Lewis acid, and molecular oxygen in an inert solvent. Polymerization is carried out using a catalyst system consisting of a combination of a catalyst component soluble in an inert solvent and an organometallic compound (B) from Groups 1 to 2 of the periodic table. This is a method for producing a cycloolefin polymer characterized by the following.

Specifically, it is a reaction product obtained by reacting the catalyst of the present invention with a tungsten salt, a Lewis acid, and molecular oxygen in an inert solvent.

The catalyst is easy to manufacture; a mixture of tungsten salt and Lewis acid is added to an inert solvent while blowing molecular oxygen or a gas containing molecular oxygen, such as air, heated and stirred, and then the excess solid component is removed. Use a solution that has been filtered out, or
Alternatively, the supernatant liquid may be used.

The catalyst obtained in this way is usually uniformly dissolved in the solvent, so there is no solid catalyst in the polymerization product, and the problem of catalyst residue, which is unfavorable in terms of the quality of the polymerization product, can be avoided, and high conversion rates can be achieved. Colorless, gel-free polymers are also obtained.

Further, if polymerization is carried out using such a small amount of catalyst, a special catalyst removal step from the polymer is generally not required, which is extremely advantageous industrially.

Inert solvents used in the above catalytic reaction include aliphatic or aromatic hydrocarbons such as n-hexane, cyclopenkune, cyclohexane, benzene, toluene, xylene, chlorobenzene, methylene chloride, chloroform, or halogenated hydrocarbons. However, the use of halogenated hydrocarbon solvents such as chlorobenzene, tetrachloroethylene, trichloroethylene, m-dichlorobenzene, 1,2 dichloroethylene gives particularly favorable results.

These inert solvents can also be used alone,
They can also be used in combination.

Further, these solvents may be different from the polymerization solvent or may be the same.

The molar ratio of the tungsten salt to the Lewis acid and molecular oxygen used in the present invention can be arbitrarily selected and is not particularly limited, but the molar ratio of the tungsten salt to the Lewis acid is usually 1.
-50, and usually converts tungsten salt into a catalyst component with a high yield of 70 V or more.

The amount of active catalyst contained in the inert solvent varies depending on the properties of each component used, solvent, temperature, time, and other aging conditions.

The aging temperature and time vary depending on the inert solvent used, but heating at 50 to 250'C for several hours is sufficient as it is easy to handle.

Of course, heating at a higher temperature or for a longer time will not cause any inconvenience.

The cycloolefin referred to in the present invention is a cyclic hydrocarbon having 4 to 5 carbon atoms or 7 or more carbon atoms, and is a compound having at least one carbon-carbon double bond in the ring.

For example, cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, 1
, 5.9-cyclododecatriene, norbornene, norbornadiene, dicyclohentasiene, etc., and these olefins may have an alkyl group, an aryl group,
It may be substituted with halogen, cyano group, ester group, etc.

Examples include 5-chloronorbornene and 5-cyanonorbornene.

Moreover, such cycloolefins can be homopolymerized or copolymerized with each other.

In the polymerization of cyclopentene, for example, as seen in the above-mentioned Japanese Patent Publication No. 43-26631, a catalyst component prepared through molecular oxygen in the presence or absence of tungsten hexachloride and aluminum chloride under the polymerization conditions. In a catalyst system made of an organoaluminum compound, polymerization does not occur even when 1 mole of tungsten catalyst solution (monomer/tungsten = io, ooo) is added to 10,000 moles of cyclopentene (Comparative Examples (1) and (2)).

However, surprisingly, in the catalyst system of the present invention, cyclopentene polymerizes very quickly even when 1 mole of tungsten catalyst solution is added to 100,000 moles or more of cyclopentene.

This clearly shows the characteristics of this catalyst system,
This is thought to be because a Lewis acid such as aluminum chloride and molecular oxygen form a special type of oxygen complex with tungsten, indicating that this is a completely new catalyst, different from conventional catalyst systems.

Regarding the color tone of the active catalyst solution in the present invention, a color in the red to dark red state usually has the highest activity, but even in the case of a color around yellow, polymerization proceeds rapidly.

For example, when 1 mole of tungsten catalyst solution is added to 100.000 moles or more of cyclopentene, the color of the reaction solution is yellow to pale pink, but polymerization proceeds extremely quickly.

Although it is possible to polymerize cycloolefins using only the above-mentioned catalyst components, the above-mentioned soluble catalyst components are usually used in consideration of problems such as stereoregularity of the polymerization product, polymerization yield, polymerization rate, and gel formation. By combining the organometallic compound (2) of Groups 1 to 2 as a polymer, industrially useful highly stereoregularity is maintained, the yield is increased, the polymerization rate is fast, and the catalytic efficiency is higher than previously predicted. The more expensive it was,
Furthermore, gel formation is also suppressed.

Tungsten salts used in the present invention include hahalides, oxyhalides, etc., such as WC16, W
OC,t, ,W,B r6 ,wo□c 12+WC
l2. WF6. A known tungsten salt such as Wl is used.

The organometallic compound is selected from the organometallic compounds of Groups 1 to 2, such as organoaluminum compounds and organotin compounds, but organoaluminum compounds are industrially preferable, and the following compounds may be mentioned. However, it is not limited to this.

For example, C2H5AlCl2゜(C2H3) 2 AI
Cl*(C2His) a A12C',.

C2H, AlBr2. (C2H,)2AIBr t
(C2Hs)aAl.

(C4Hg) BA lt(lso C4Hg
) 3A 1, etc., and mixtures thereof also give good results.

As the Lewis acid used in the present invention, aluminum chloride, aluminum bromide, aluminum iodide, tin tetrachloride, etc. are selected, but it is preferable to use aluminum chloride from a handling and industrial standpoint.

The molar ratio of tungsten salt to Lewis acid such as aluminum chloride and molecular oxygen can be arbitrarily selected and is not particularly limited, but the molar ratio of tungsten in the soluble polymer to the organometallic compound is It is an important factor that controls regularity, polymerization yield, polymerization rate, etc., and is 0.1 to 1000 mol per 1 mol of tungsten, preferably 1
It is sufficient to select the amount within the range of 200 mol, but is not particularly limited thereto.

In the present invention, polymerization is initiated by dissolving a cycloolefin in an inert solvent and adding an organometallic compound to a soluble catalyst of a reaction product consisting of a tungsten salt, a Lewis acid, and molecular oxygen.

The inert solvent is selected from aliphatic and aromatic hydrocarbons or halogenated hydrocarbons such as n-hexane, cyclopenkune, cyclohexane, benzene, toluene, xylene, chlorobenzene, methylene chloride, etc., and mixtures thereof are used. However, there is no inconvenience in installing it separately.

Furthermore, in the present invention, cycloolefins can be polymerized even in the absence of such diluents such as inert solvents.

The polymerization temperature can be selected within the range of -70°C to 70°C, but industrially it is preferably carried out at about -30°C to 50°C.

The catalyst thread of the present invention has extremely high activity and is characterized by providing a gel-free soluble polymer with highly stereoregularity, but it is difficult to actually carry out the method of the present invention industrially. For example, it can be carried out by sequentially adding a solvent, a sulfuric acid and a tungsten catalyst, cooling the polymerization reactor to a predetermined polymerization temperature, and then adding an organoaluminum compound, but the order of addition can be selected arbitrarily.

As for the post-processing method, any known method can be used.

The cyclopentene homopolymer and copolymer with other components obtained by this polymerization method are rubber-like elastomers with heat aging resistance and physical properties very similar to natural rubber, so they are very suitable as tire or industrial rubbers. It has important value.

In addition, other cycloolefin polymers each have a unique structure and are of industrial interest.

The present invention will be specifically described below with reference to Examples.

Example 1 (a) Catalyst Preparation In a four-bottle flask equipped with a vacuum stirrer, a thermometer, an oxygen gas inlet tube, and a condenser, 300 ml of chlorobenzene, 9.9 (22.9 mmol) of tungsten hexachloride, and 7.9 mL of aluminum chloride were placed. After adding 7f;1 (57,8 mmol),
Reflux at 150° C. for 5 hours in a nitrogen gas atmosphere while blowing dry pure oxygen gas.

Pure oxygen gas was blown in for 1 hour.

After the temperature is returned to room temperature, it is filtered under a nitrogen gas atmosphere to remove solid residues, and then subjected to polymerization.

The catalyst solution thus obtained had a dark red color, the tungsten concentration was 0.0634 mmol/yd, and the aluminum concentration was o,tos mmol/T/Ll.

The conversion rate of tungsten hexachloride was 83%.

(b) Polymerization of cyclopentene Polymerization was carried out in an ultra-high purity nitrogen atmosphere using a stirrer, a nitrogen inlet tube, and a flask into which the sample could be injected.
1 and 0.60 ml of the catalyst solution of Example 1(a)
(equivalent to 0.0378 mmol of tungsten) was added.

(Monomer/Tungsten-30,000/1) The color tone of the solution is dark red.

After standing at room temperature for about 1 hour, the polymerization vessel was cooled to -10°C, and 0.3% of ethylaluminum dichloride was added thereto.
Add 78 mmol dropwise.

Polymerization proceeds surprisingly slowly, while the polymerization temperature is maintained between -10°C and 0°C.

After 3 hours, the polymerization is stopped with monoethanolamine and an antiaging agent is added, followed by reprecipitation and purification with methanol.

The polymer thus obtained is dried until the solvent is sufficiently removed.

The weight of the product was 63 g and the conversion was 81 V.

Further, it was found by infrared absorption spectrum that this polymer had a structure containing a 92 chain tramess double bond and an 8 chain cis double bond.

The intrinsic viscosity in toluene was 2.55 at 25°C.

Comparative Example 1 The experimental method was as described in Example 1(b), but as a comparative experiment, 8 tungsten hexachloride (0.02 mmol) was dissolved in 501 rLl of chlorobenzene, and oxygen gas was further blown into the solution.

Furthermore, 17.51 rLl (13.6 g) of cyclopentene was added (monomer/tungsten - 10,000), and after standing at room temperature for about 1 hour, the polymerization vessel was cooled to -10°C.

0.2 mmol of ethylaluminum dichloride was added dropwise to the solution to initiate polymerization, but no polymerization product was obtained even after 10 hours.

Comparative Example 2 This comparative example is an example in which a catalyst was prepared in the presence of aluminum chloride.

The experimental method was as described in Example 1(b), but as a comparative experiment, 10 μm (0.025 mmol) of tungsten hexachloride and 20 μm (0.15 mmol) of aluminum chloride were dissolved in 66 yd of chlorobenzene, and further oxygen gas was added. Infuse.

Furthermore, 21.9 ml (1 rg) of cyclopentene (monomer/tungsten = 10.000/1) is added, and after being left at room temperature for 1 hour, the entire container is cooled to -10°C.

0.25 mmol of ethylaluminum dichloride was added dropwise to the solution to initiate polymerization, but no polymer was obtained even after 10 hours.

Example 2 In this example, the catalyst of Example 1(a) was used to react under the conditions described in Example 1(b), but toluene was used as the polymerization solvent and triisobutyl was used as the organoaluminum compound. Use aluminum.

100 ml (7,7,8 g) cyclopentene, 30
01'nl of toluene, 0.05 mmol of tungsten catalyst solution, 0.227 mmol of triisobutylaluminum are used.

Monomer/tungsten-20,000, triisobutylaluminum/tungsten-4.

The weight of the obtained polymer was 64 g, and the conversion rate was 82%.

According to the infrared absorption spectrum, this polymer had 92.2% of tramethane double bonds and 7.8% of cis double bonds.

Further, the intrinsic viscosity in toluene at 25°C was 2.50.

Example 3 This example is carried out in a manner analogous to that described in Example 1(b) using the catalyst of Example 1(a).

100ml (77.8g) of cyclopentene 300T
L1 of chlorobenzene, 0.0114 mmol of tungsten catalyst solution, 0.228 mmol of ethylaluminum dichloride are used.

Monomer/tungsten = ioo, ooo ethylaluminum dichloride/tungsten = 20.

The weight of the obtained polymer was 51.9, and the conversion rate was 65.

The infrared absorption spectrum revealed that this polymer had 89 tramethane double bonds and 11 cis double gold bonds.

Further, the intrinsic viscosity at 25° C. in toluene is 5.90.

Example 4 This example shows a method for producing a copolymer of cyclopentene and 1,5-cyclooctadiene.

The experiment was carried out in the same manner as in Example 1(b), with 1 ood (77.8 g) of cyclopentene and 5 ml (4,41 and 4001 rLl of chlorobenzene) of 1.5 cyclooctadiene
into a flask to prepare 0.1 of the catalyst solution of Example 1(a).
8rILl (0.0114 mmol of tungsten) was added, (monomer/tungsten = 100.000), and after being left at room temperature for about 1 hour, the polymerization vessel was cooled to -10°C.
0.228 mmol of ethylaluminum dichloride is added dropwise into this.

Polymerization was started immediately and 4 hours later, the polymerization was stopped with monoethanolamine and purified by reprecipitation in methanol.

The polymer thus obtained was 55I with a conversion rate of 67.

Further, the intrinsic viscosity at 25° C. in toluene was 4.75.

Example 5 This example shows an example in which a catalyst was prepared by blowing air instead of oxygen gas.

In a similar manner to Example 1(a), tungsten hexachloride 9.2
g (23.4 mmol) and aluminum chloride 12.4
．． 9 (93.6 mmol) of chlorobenzene 4007
7171! Add it inside and blow dry air into it.
React at 50°C for 4 hours.

Air was allowed to react for 1 hour. The solid residue is used as a catalyst for post-purification polymerization.

The catalyst solution thus obtained had a dark red color and was found to have a tungsten concentration of 0.0439 mmol/ml and an aluminum concentration of 0.0834 mmol/1711.

The conversion rate of tungsten hexachloride was 75%.

Example 6 Using the tungsten catalyst obtained in Example 5, the polymerization of cyclopentene is carried out in the manner described in Example 1(b).

Cyclopentene 100ml (77.8g), toluene 3
0.52 ml of the catalyst solution of Example 5 (equivalent to 0.0227 mmol of tungsten) is added to 00rILl.

(Monomer/Tungsten-50,000) After standing at room temperature for about 1 hour, the polymerization vessel is cooled to -10°C and a mixture of 0.114 mmol of triethylaluminum and 0.0681 mmol of triisobutylaluminum is added.

The reaction proceeds very rapidly and is stopped after 4 hours and subjected to the treatment method described above.

The thus obtained polymer had a conversion rate of 60.9 and a conversion rate of 77.

From the infrared absorption spectrum, it was found that it has 90% trans and 10 cis combinations.

The intrinsic viscosity in toluene at 25°C was 3.62.

Claims (1)

[Claims] 1 A cycloolefin, which is a cyclic hydrocarbon compound having 4 to 5 carbon atoms or 7 or more carbon atoms and has at least one carbon-carbon double bond in the ring, is reacted with a tungsten salt, a Lewis acid, and molecular oxygen in an inert solvent. Polymerization using a catalyst system consisting of a combination of a catalyst component (5) that is soluble in an inert solvent and an organometallic compound (2) from Group 1 to Group II of the periodic table. A method for producing a cycloolefin polymer, characterized by: