JPS60197708A - Method for producing rubbery copolymer - 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 the production of a rubber-like copolymer (hereinafter abbreviated as EPDM) consisting of ethylene, α-ole, and non-conjugated diene using a slurry polymerization method. This invention relates to a method for increasing the reaction rate of dienes. It is known that sulfur-vulcanizable EPDM can be produced by copolymerizing ethylene, an α-olefin, and a nonconjugated diene using a catalyst consisting of an organoaluminum compound and a vanadium compound.

However, the nonconjugated diene compounds used here to enable sulfur vulcanization generally have low reactivity and high boiling points. Therefore, a considerable amount of energy is consumed in separating the unreacted non-conjugated diene from the polymerization product. Further, if a large amount of unreacted non-conjugated diene remains in the copolymer, it not only deteriorates the physical properties but also generates a strong odor, which significantly impairs the working environment in the manufacturing process, especially in the finishing process. On the other hand, the reaction rate of non-conjugated dienes is particularly low in slurry polymerization, in which the polymer is precipitated in a poor solvent, and this has been a major obstacle to taking advantage of the many advantages of the slurry polymerization method. In view of this situation, the present inventors have intensively researched a method of increasing the reaction rate of non-conjugated dienes using a slurry polymerization method, and as a result, they have devised a method for forming active species using conventionally known compounds. In addition, the present invention has been achieved by discovering that even with a slurry polymerization method, an excellent effect of significantly increasing the reaction rate of non-conjugated dienes can be obtained.

The method for producing an olefin copolymer of the present invention includes ethylene, α
→A male copolymer consisting of a reflexine and a non-conjugated diene is produced by a slurry polymerization method by bringing a vanadium compound and an organoaluminum compound into contact in advance in the absence of the monomer). The method is characterized in that a seeded catalyst is supplied to a polymerization reaction zone in which a monomer is present to initiate polymerization.

According to the method of the present invention, since the microstructure of the produced copolymer does not change, the reaction rate of non-conjugated diene can be significantly improved without deteriorating the quality of the copolymer.

The present invention will be explained in more detail below.

α-olefins have 3 to 12 carbon atoms, specifically propylene, 1-butene, 4-methylpentene-
Among them, propylene and 1-butene are preferred. In addition, the following compounds can be used as non-conjugated dienes: dicyclopentadiene, tricyclopentadiene, 5-methyl-2
, 5-nor is nashiene #5-methylene-2-norgornene, 5-ethylidene-2-norgornene j5-isopropylidene-2-norgorene, 5-isothropene A-2
-nor is runene, 5-(1-)7-nyl)-2-norgyrunene, cyclooctadiene, vinylcyclohexane, 1,5.9-cyclododecatriene.

6-methyl-4,7,8,9-tetrohydroindene,
2-2-dicyclopentenyl, trans-1,2-/
vinylcyclobutane, 1.4-S, xadiene, 2-
Examples include methyl-1,4-%xadiene and 1,6-octadiene, among which 5-ethylidene-2-nor is preferably runene (ENB) and dicyclopentadiene (DCP).

Next, triethylaluminum and triisobutylaluminum are used as organoaluminum compounds which are one of the components for forming catalytically active species.

Trialkyl aluminum such as trioctyl aluminum: diethyl aluminum monochloride.

Dialkyl aluminum monohalides such as diethyl aluminum monobromide and diisobutyl aluminum monochloride: ethyl aluminum sesquichloride,
Alkylaluminium sesquihalides such as ethylaluminum sesquibromide, isobutylaluminum sesquibromide, n-butylaluminum heptaquibromide, etc. can be used, and among these compounds, diethylaluminum monochloride (DIAC), ethylaluminum sesquichloride (EASc) are Particularly preferred.

The other vanadium compound for forming active species is vanadium tetrachloride.

Vanadium oxytrichloride, vanadium triheptylana7tonate, oxyvanadium diacetylacetonate,
or the reaction product of vanadium chloride and alcohol, vanadate triethoxide, vanadate tri-n
-butoxide, panadate di-n-butoxide, vanadate ethoxy chloride, and the like. Among these compounds, oxyvanadium chloride, the reaction product of vanadium oxytrichloride and an alcohol, and oxyvanadium diacetylacetonate are particularly preferred.

Next, the solvent used in the slurry polymerization according to the present invention is, for example, propylene! -butene, methylene dichloride, methylene dibromide, ethyl chloride, and mixtures thereof, but propylene and 1-butene, which are also reaction monomers, are particularly preferred.

In addition, in order to form active species, the vanadium compound and the organoaluminum compound can be brought into contact in the absence of a monomer by dissolving or diluting one component in an inert organic solvent and adding the other component. This is done by adding the ingredients and contacting them.

In this contact method, one component is dissolved or diluted in a suitable container, and the other component is added thereto.

A batch operation may be followed in which the active species are mixed to form and then fed to the polymerization reactor, or polymerization may be carried out by continuously contacting the solution or diluted solution of the vanadium compound and the solution of the organoaluminum compound in a pipe. Continuous operation may be followed in which the reactor is fed with active species.

However, when relying on the latter continuous operation, it is preferable to carry out the contact under high shear conditions using a line mixer or the like, since the active species formed will be homogeneous. The temperature when bringing the organoaluminum compound and vanadium compound into contact is usually -60°C.
~100°C, preferably -40~50°C. The contact time (that is, the time from contact of both components until they are subjected to a copolymerization reaction) is preferably as short as 30 minutes, particularly preferably as short as 5 minutes. If the time exceeds 30 minutes, the activity may decrease significantly.

Inert organic solvents used for contacting are intane, hexane, heptane, octane, and nonane.

Examples include cyclohexane, benzene, toluene, xylene, etc., with toluene being particularly preferred. In forming the above-mentioned active species, the amount of the organoaluminum compound used is 1 to 100 times, preferably 2 to 30 times, per mole of the vanadium compound. The polymerization reaction temperature is -50 to 10
0°C, preferably -20 to 60°C.

Next, the present invention will be described in more detail based on Examples.

Although the polymerization method described in the Examples is batch polymerization, the present invention is not limited to this, but can also be applied to continuous polymerization.

Example 1 (1) Formation of active species Active species were formed from an organoaluminium compound and a vanadium compound in the following manner.

A sufficiently dried flask was purged with nitrogen, and 50 mJ of toluene, which had been dried and degassed with moleki and sieves, was added, and 1.0 m of vanadium trichloride (VOCl2) was added.
mol was added, thoroughly stirred, and the temperature was controlled to be constant at 10°C. Next, diethylaluminum monochloride (
15.0 mmol of DEAC) was added, and the temperature was maintained at 10°C while stirring. In the flask, active species were formed in the form of a brown, extremely small precipitate.

(2) Polymerization operation A stirring blade, a gas blowing tube, a thermometer, a pressure needle, a non-conjugated diene supply tube, and a catalyst supply tube were attached to a 3-ton autoclave, and the autoclave was sufficiently purged with nitrogen and dried. Into this autoclave was placed 1.6 liters of dry sitapropylene in liquid form. Through the gas blowing pipe, the pressure inside the autoclave is 9.5kl.
Dry ethylene and hydrogen were bubbled through the reactor so that l/l, i'a remained constant. The amount of hydrogen aeration is 1/20 mo of ethylene.
1- Maintained constant. The temperature of the autoclave was kept constant at 10° C. by an external jacket. Next, add ENB to 5. O
gr was added and thoroughly stirred.

After that, the active species was set to 0.34 mm as VOCj3.
ol was added to start copolymerization. The time from contacting DEAC and VOCT5 to form active species to subjecting the active species to the copolymerization reaction (hereinafter abbreviated as "contact time between aluminum compound and panadium compound") was 6 seconds. Ta.

During polymerization, the pressure was 9.5 k11/yB” Ga the temperature was 1
The temperature was controlled to be constant at 0°C. 30 minutes after the start of polymerization, the supply of ethylene and hydrogen was stopped, and methanol was added at 100 mA.
The polymerization reaction was stopped by adding t.

Next, add a small amount of anti-aging agent, stir thoroughly, remove ethylene, propylene and hydrogen, and steam strip. After drying, yield, Mooney viscosity, propylene content, and iodine number are measured. The results are summarized in Table-1.

As an index for comparing the reaction rate of non-conjugated diene, the value calculated by the following formula was used.

That is, the larger the value of R, the higher the reaction rate of the nonconjugated diene.

Example 2 (1) Formation of active species Formation of active species was carried out at -30°C, and other conditions were exactly the same as in Example 1.

(2) Polymerization operation Copolymerization was carried out under the same conditions as in Example 1, and analysis was conducted.

However, the contact time between the aluminum compound and the vanadium compound was 4 minutes.

The results are summarized in Table-1.

Example 3゜(1) Formation of active species The vanadium compound was changed to oxypanadium diacetyl acetate) (VO(AcAc)2), and the other conditions were as in Example 1.
Active species were obtained under the same conditions.

(2) Polymerization operation Copolymerization was carried out under the same conditions as in Example 1, and analysis was conducted. However, the contact time between the aluminum compound and the vanadium compound was 18 seconds. The results are summarized in Table-1.

Example 4゜ (1) Formation of active species Active species were obtained under exactly the same conditions as in Example 1.

(2) Polymerization operation Using DCP as a nonconjugated diene in 8. Ogr was added and hydrogen was aerated at a 1/6 molar ratio of ethylene to carry out copolymerization. Other polymerization operating conditions were the same as in Example 1. Award, the contact time between aluminum compound and vanadium compound is 1
It was 1 second.

The results are summarized in Table -1.

Comparative Examples 1 to 4 below are examples in which a vanadium compound and an organoaluminum compound were brought into contact in the presence of a monomer.

Comparative Example 1 Using the same autoclave as in Example 1, copolymerization was carried out in the following manner. Pour 1.6 m of dry propylene in liquid form into a dry autoclave, pass through the gas blowing pipe, and add dry phosphorus to the autoclave so that the pressure inside the autoclave remains constant at 9.5 kg (H). The amount of hydrogen aeration was kept constant at 1/29 mol of ethylene.

The temperature of the autoclave is 10℃ depending on the external rack.
kept constant. Next, add ENB to 5. Ogr was added and thoroughly stirred, and DEAC (5.1 mmol 1) was added and thoroughly stirred. After that, 0.34 mmol of voct5 was added to start copolymerization. During the polymerization, the pressure was controlled at 9.5 kVcrR2G' temperature at a constant 10°C. 30 minutes from the start of polymerization
After several minutes, the supply of ethylene and hydrogen was stopped. The subsequent operations were performed in the same manner as in Example 1, and analysis was performed. The results are summarized in Table-1.

Comparative Example 2゜In Comparative Example 1, 1ilWB was changed to 5. After adding Ogr and stirring thoroughly, 0.34 mmol of voct5 was added and thoroughly stirred. After that, 5.1 mmol of DBAC was added and the copolymerization was started at a pressure of 9.5I false 2Q.
Control the temperature at a constant 10°C, and wait 30 minutes from the start of polymerization.
After several minutes, the supply of ethylene and hydrogen was stopped. Other conditions and subsequent operations were the same as in Comparative Example 1, and analysis was conducted. The results are summarized in Table-1.

Comparative Example 3 In Comparative Example 1, the nonadium compound was changed to oxyvanadium cyano7tylacetonate (VO(AaAa)2), and 0.34 mmol of this was added to start copolymerization.

The analysis was conducted under the same conditions as in Comparative Example 1.

The results are summarized in Table-1.

Comparative Example 4 In Comparative Example 1, the non-conjugated diene was changed to DCP and 8.0 gr of this was added, and hydrogen was 1/6 mol of ethylene.
The copolymerization was carried out by aerating at a low temperature. Other polymerization operating conditions were the same as in Comparative Example 1. The results are summarized in Table-1.

From Table 1, it can be seen that the methods of Examples 1 to 4, in which the active species in which the vanadium compound and the organoaluminium compound are brought into contact with each other in advance in the absence of a monomer, are supplied to the polymerization zone to initiate polymerization, It is clear that the anti-6 ratio has improved. In addition, in Example 4 in which the type of non-conjugated diene was changed, the reaction rate of the non-conjugated diene was slightly lower than in other Examples 1 to 3, but the contact treatment was not performed in the absence of a monomer. When compared with Comparative Example 4, it can be seen that the method of Example 4 is superior.

Claims (1)

[Claims] When producing a rubbery copolymer consisting of ethylene, α-olefin, and non-conjugated diene using a slurry polymerization method, a vanadium compound and an organoaluminum compound are brought into contact in advance in the absence of a reactive monomer. A method for producing an olefin copolymer rubber, characterized in that a catalyst in which active species have been formed is supplied to a polymerization reaction zone in which a monomer is present to initiate polymerization.