JPH03220212A - Solid catalyst component for production of ethylene/ propylene copolymer rubber - Google Patents

Abstract

PURPOSE:To obtain the title catalyst component which can give an ethylene/propylene copolymer rubber not requiring any deashing step by bringing a solid product containing Mg and Ti compounds and obtained by a specified process into contact with xylenol and TiCl4 at a specified temperature. CONSTITUTION:A homogeneous solution is prepared by bringing diethoxymagnesium into contact with 0.5-2ml, per g of the diethoxymagnesium, of tetrabutoxytitanium in the presence of xylenol at a temperature between 50 deg.C and the boiling points of the above substance. This solution is further brought into contact with an aromatic carboxylic acid chloride and TiCl4 at a temperature between 60 deg.C and the boiling points of the substance, and the obtained solid product is further brought into contact with xylenol and TiCl4 at a temperature between 60 deg.C and the boiling points of the substances to obtain the title catalyst component. When the title copolymerization is performed in the presence of the above catalyst component, a highly uniform rubberlike copolymer which has a high randomness and does not require any deashing step because the content of catalyst residues can be decreased to a very low level because of high catalyst activity and is highly safe because no V compound is contained can be obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides that when subjected to ethylene-propylene copolymerization,
The present invention relates to a high-performance solid catalyst component capable of obtaining a copolymer rubber in which ethylene and propylene are randomly polymerized in a high yield. The copolymer produced using the catalyst component of the present invention is widely used in fields that require PM resistance, water resistance, and impact resistance, such as industrial products such as hoses and packing necks, electric wire cables, and footwear. . It is also used to modify resins made of polypropylene.
For example, it is applied to automobile bumpers and films.

[Conventional technology] Conventionally, as a catalyst for producing ethylene-propylene copolymer rubber, a catalyst based on a combination of a vanadium compound soluble in a solvent during polymerization and an organic aluminum has been mainly used. Since the polymerization activity of the catalyst is low at high temperatures, polymerization is carried out at low temperatures.

On the other hand, in Ziegler catalysts whose active components are transition metal compounds such as titanium halides, the catalytic activity when used for the homopolymerization of ethylene or propylene is improved by using a carrier such as magnesium chloride to form a supported catalyst. Many proposals have been made to dramatically improve the performance. However, when such titanium-based catalysts are used for copolymerization of ethylene and propylene,
It is very difficult to obtain random copolymers of ethylene and propylene in high yields.

[Problem to be solved by the invention] When a vanadium-based catalyst is used for ethylene-propylene copolymerization, the yield of polymer per vanadium state (hereinafter referred to as catalyst activity) is low, and the amount of polymer contained in the resulting copolymer rubber is low. Since the proportion of residual catalyst is large, a step for removing and decolorizing the catalyst residue (deashing step) is unavoidable. Since this deashing process uses multiple alcohols or chelating agents, a recovery device or regeneration device for them is indispensable, and there are many problems associated with III sources, energy, etc., and those skilled in the art would like to solve them as soon as possible. It was an important rj4#. Furthermore, since the polymerization reaction is carried out at a low temperature, it is difficult to remove the heat generated during polymerization, which causes many problems in terms of process design and operation. Furthermore, since vanadium has durability, it can be said that it is not preferable as a catalyst component when considering the safety of the copolymer rubber produced.

In order to solve the above-mentioned deadlock point, as a recent trend, many methods have been disclosed for obtaining ethylene-propylene random copolymers at high yields using titanium-based supported catalysts.

However, copolymers obtained with titanium-based catalysts have poor randomness and a large proportion of long chain moieties of ethylene and propylene, making it extremely difficult to obtain rubber-like copolymers. I had a lot left. The ethylene-
Among the titanium-based catalysts proposed for propylene copolymerization, the mainstream is a system using magnesium salt as a carrier material, but in addition to poor random polymerization properties, the catalytic activity is far from sufficient. Moreover, the chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage of having an adverse effect on the produced copolymer, similar to the chlorine in titanium halides. - The problem remains that a perceptibly high activity is not achieved, or that the concentration of magnesium chloride itself must be kept low.

The present inventors proposed a catalyst component using a dialkoxymagnesium compound as a starting material as a catalyst for use in Arashi polymerization of olefins, for example in JP-A-62-158704, and achieved extremely high catalytic activity. did.

When this catalyst composition was subjected to ethylene-propylene copolymerization, it was possible to maintain extremely high catalytic activity in homopolymerization as intended, but the resulting copolymer contained ethylene and propylene. It was not possible to obtain a rubber-like copolymer with high random polymerizability in a high yield due to the large amount of long-chain parts. Therefore, as a result of our earnest efforts to solve the problems remaining in the prior art by further improving the method for producing the catalyst composition, we have arrived at the present invention, which we propose to Su.

[Means for Solving the Problems] That is, the present invention is characterized by: (a) jetoxymagnesium in the presence of (b) xylene (a) 0.5 m/g jetoxymagnesium
l or 2 ml of (C) tetrabutoxy titanium and 50
A homogeneous solution is prepared by contacting at a temperature above 60°C and below the boiling point of each substance, and this is further mixed with (d) aromatic carboxylic acid chloride and (e) titanium tetrachloride at a temperature above 60°C below the boiling point of each substance. The resulting solid product is further treated with (b) xylene and (e) titanium tetrachloride.
The object of the present invention is to provide a solid catalyst component for producing ethylene-propylene copolymer rubber, which is obtained by contacting each substance at a temperature of 0°C or higher and lower than the boiling point of each substance.

(b) Xylene (
Hereinafter, it may be referred to as (b) substance.

) include 0-xylene, m-xylene, and p-xylene, among which 0-xylene is particularly preferred.
It's xylene. It is also possible to use a mixture of these in any proportion.

Examples of aromatic carboxylic acid chloride (d) (hereinafter sometimes referred to as the substance (d)) conveniently used in the present invention include benzoic acid chloride, tortoic acid chloride, and phthalic acid chloride.

The solid catalyst component obtained in the present invention constitutes a catalyst for producing ethylene-propylene copolymer rubber by using it in combination with an organoaluminum compound. The aluminum compound used in this case has the formula: RnA
It is represented by I X3-n (where R is a hydrocarbon group, X is a halogen atom, and l≦n≦3). Specifically, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, etc. may be mentioned, but it is also possible to use a mixture of these.

When obtaining the solid catalyst component in the present invention, the raw material (a)
Jetoxymagnesium (hereinafter sometimes simply referred to as the (a) substance) and (C) tetrabutoxytitanium may hereinafter simply be referred to as the (c) substance. ) for (b
) The usage ratio of the substance is arbitrarily set, but usually the amount of the substance (b) is in the range of 5 to 100 ml per 1 g of the substance (a). In addition, <c> substance is (a) 0.5 per 1 g of substance
It is necessary to use the amount in a range of ml or more and 2 ml or less.

Contact of (&) substance, (b) substance and (C) substance is 5
It is necessary to conduct the reaction at a temperature of 0°C or higher and lower than the boiling point of each substance, and the contact time is usually in the range of 5 minutes or more, preferably 1 hour or more. If the contact temperature is below 60° C., the reaction will not proceed sufficiently, and if it exceeds the boiling point, the solvent will evaporate, making it difficult to control the reaction and making it impossible to form a homogeneous solution.

As described above, a colorless and transparent homogeneous solution is obtained, which is brought into contact with (d) substance and (e) titanium tetrachloride (hereinafter referred to as (e) v!J quality). ,
A solid catalyst component is produced by further repeated contact with the substance b) and the substance (e). At this time, (a
)11! For 1g of Iiiij, (d) substance is 0.0
(e) the substance is in the range of 10 to 100 g;
It is preferable to use the range of m1. (a) substance;
(b) the substance and (c) the reaction product obtained from the substance and (
d)! The contact with the substance and (e) substance is optional, but the contact needs to be carried out at a temperature of 60° C. or above and below the boiling point of each substance, and is usually carried out at an acoustic range of 5 minutes or more and 50 hours. If the contact temperature is below 60°C, the reaction will not proceed sufficiently, and if it exceeds the boiling point of each raw material, the solvent will evaporate, making it difficult to control the reaction. In addition, when preparing the solid catalyst component, n-
It is also possible to wash using a diluent solvent such as hebutane or n-hexane.

The slowing component produced as described above is combined with the organoaluminum compound to form a catalyst for producing ethylene-propylene copolymer rubber. The organoaluminum compound used is used in a molar ratio of 1 to 1000 per mole of titanium atoms in the catalyst component.

Usually, polymerization involves hydrocarbon or halogen 4? , carried out in a hydrocarbon solvent, the polymerization temperature is 0~150℃, and the polymerization pressure is 0~100 kg/cn+2·G. The partial pressures of ethylene and propylene are arbitrarily adjusted so that the ethylene content in the resulting copolymer is between 10 and 70 wt%.

For ethylene-propylene copolymerization, P-
It is also possible to add an electron-donating compound such as methyl torutoate, and an ice pack can be used if necessary to adjust the molecular weight of the copolymer.

[Example] The present invention will be specifically explained below using practical examples.

Example 1 Preparation of solid catalyst component
Jetoxymagnesium 5 ml in a 0 ml round bottom flask
A homogeneous solution was obtained by adding 5 ml of tetrabutoxytitanium in portions to this suspension and reacting at 70° C. for 2 hours. This solution was mixed with 100 ml of titanium tetrachloride at 100°C, which was charged into a separately prepared 500 ml round bottom flask.
Benzoic acid chloride Fl was added dropwise to 1 over 1 hour.

Added Oml. Next, the temperature in the system was raised to 110° C., and the reaction was carried out with stirring for 2 hours. Thereafter, it was washed three times with 100 ml of xylene at 80° C., and after removing the supernatant liquid, 50 ml of xylene was charged again to obtain a suspended J solution. Furthermore, titanium tetrachloride 2, which had been kept at 100°C in advance, was added to the suspension.
The mixture was pumped into a mixed solution of 0 ml and 30 ml of xylene, heated to 110° C., and reacted with stirring for 2 hours. Thereafter, a solid catalyst component was obtained by washing 10 times with 100 ml of hebutane at 40°C. The titanium content in this solid catalyst component was 5.3% by weight.

Polymerization> Charge 200 ml of n-hebutane into a separable flask equipped with a stirrer and have an internal volume of 300 ml, which has been completely purged with a mixed gas of ethylene and propylene. .7 mmol and 0.28 mmol of methyl p-)ruylate were charged. The flow rates of ethylene and propylene were 1.01/min and 0.8/min, respectively.
1/min, and after raising the temperature in the system to 60°C, the solid catalyst component was added to 0.017 mmol as titanium atom.
The polymerization was carried out at normal pressure for 15 minutes while maintaining the temperature at 60°C. The polymerization was terminated by adding 2 ml of ethanol, and the resulting copolymer suspension was further introduced into 600 ml of ethanol and then 10 ml of hydrochloric acid.
was added and stirred overnight. The obtained solid copolymer was separated by filtration, heated to 80°C, and dried under reduced pressure to obtain 5.5 g of polymer.The activity per 1 g of catalyst at 0 polymerization time of 15 minutes was 360 IC/g-cat-. Yes, 13C-NM
As a result of analysis by R, the propylene content in the above copolymer was 51% by weight, and the random fraction was 53%.

Example 2 Phthalic acid chloride instead of benzoic acid chloride 1.
An experiment was conducted in the same manner as in Example 1 except that Oml was used. The titanium content in this solid catalyst component was 3.3% by weight. The activity per gram of catalyst at a polymerization time of 15 minutes was 180 g/g-cat, 13c.
As a result of NMR analysis, the propylene content in the copolymer was 60% by weight, and the random fraction was 54%.

[Operations and Effects of the Invention] When ethylene-propylene copolymerization is carried out using the catalyst component obtained by the present invention, since the catalyst has extremely high activity, the catalyst residue in the produced copolymer can be kept to an extremely low level. Moreover, since the amount of residual chlorine is so small, the effect of chlorine on the produced copolymer can be reduced to the extent that no deashing step is required at all. In addition, since the solid catalyst component does not contain toxic vanadium compounds,
The solid catalyst component itself and the resulting copolymer are highly safe. In addition, when the solid catalyst component of the present invention is used, a rubber-like copolymer with high random polymerizability and high uniformity without a black-forming polymer can be obtained.

[Nuclear magnetic resonance spectrum (13C-NMR) preparation method]
In the Wood Example, the composition and randomness of the ethylene-propylene copolymer obtained using the solid catalyst component were analyzed by 13 cm NMR. 0 with a volume ratio of 9 to 1
- Several drops of hexamethyldisiloxane were added as a reference substance to 2 ml of a mixed solution of dichlorobenzene and heavy henzene, and about 200 mg of the copolymer was heated to 100 to 140° C. to dissolve it, thereby preparing a measurement sample. For measurement, JEOL Ltd. IIJNM-GSX-27 using the pulse Fourier transform method was used.
Measurements were made using Type 0 with a pulse interval of 7 seconds.

The assignment of each peak is as reported by C., J., Carman et al. (Macrowolecules * Vol. 10, 53
6 (1977)), the composition of the copolymer was G.
.

The method of J. Ray et al.
s Volume 10.

773 (1977)) from the three chain length (triad) distribution of ethylene and propylene monomer units. Further, the randomness of the copolymer was expressed as a random fraction from the triad distribution of ethylene and propylene monomer units using the following formula.

Random fraction (%) = 100 - (PPP + EEE) where PPP and EEE are the proportions (mole percent) of triads of propylene and ethylene, respectively.

[Brief explanation of drawings]

FIG. 1 is a flowchart illustrating the invention.

Claims (1)

[Claims] (1) (a) diethoxymagnesium in the presence of (b) xylene (a) 0 per gram of diethoxymagnesium
．． A homogeneous solution is prepared by contacting 5 ml or 2 ml of (c) tetraptoxytitanium at a temperature of 50° C. or higher and lower than the boiling point of each of the above substances, and this is further mixed with (d) aromatic carboxylic acid chloride and (e) Titanium chloride and 60
It is obtained by contacting at a temperature of 60°C or higher and below the boiling point of each substance, and then contacting the resulting solid product with (b) xylene and (e) titanium tetrachloride at a temperature of 60°C or higher and below the boiling point of each substance. A solid catalyst component for producing ethylene-propylene copolymer rubber, characterized by: