JPS59105009A - Copolymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a polymer of an ethylene content which is higher than that of a polymer prepared from a monomer mixture of the same composition, by using a composite compound of a specified composition of an alpha-olefin with ethylene. CONSTITUTION:In the random and/or block copolymerization of an alpha-olefin (e.g., propylene or butene-1) with ethylene, the olefins are copolymerized by using a catalyst prepared by using a carrier which is a composite compound containing a magnesium halide, a C-O or C-N bond-containing compound and a compound having sufficient affinity for electrons to oxidize Ti<2+>; allowing this carrier to support titanium (IV or III) chloride; and combining the supported transition metal catalyst with an organometallic compound (e.g., diethylaluminum chloride). When the composite compound of the above composition is used as a carrier, it is possible to obtain a polymer of a relatively higher ethylene content even from a monomer mixture of the same composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for random and/or block copolymerization of α-olefin and ethylene.

The method of using a catalyst consisting of a supported transition metal, organoaluminium, and M organic acid ester as a polymerization catalyst for α-olefin was proposed in Japanese Patent Publication No. 39-12105, and since then many improvements have been made to the catalyst. However, both the catalytic activity and the stereoregularity of the obtained fl-polymers have been significantly improved.

〃) When α-olefin and ethylene are copolymerized using these catalysts, although the reason is not clear,
When polymerized with a monomer mixture having the same composition as compared to a TlC1-based catalyst, a polymer containing less ethylene kumquat is obtained. In the bulk polymerization method using α-olefin itself as a medium, the polymerization pressure is high, and in order to handle polymers with a high ethylene content, there are equipment problems and a large amount of unreacted α-olefin and ethylene must be recovered. There is a problem that cannot be ignored.

As a result of various studies, the present inventors have found that by using a composite having a specific composition as a carrier, a polymer with a relatively high ethylene content can be obtained even if a monomer mixture with the same composition is used. Heading Completing the Invention.

The purpose of the present invention is to carry out copolymerization of olefins.

An object of the present invention is to provide a method for producing a polymer with a high ethylene content. Namely, one object of the present invention is to provide a method for random and/or block copolymerization of α-olefin and ethylene, in which magnesium halide and C-t) or C-t) are copolymerized. Compounds containing -N bonds and Ill g! Using a complex containing a compound having sufficient electron affinity to oxidize + as a carrier,
The present invention relates to a method for copolymerizing olefins, which is characterized by using a carrier-type transition metal catalyst in which titanium chloride with a valence of 1 or 2 is supported on the carrier and a catalyst consisting of an organometallic compound.

In the method of the present invention, supported transition metal catalysts include magnesium halides, compounds containing C-U or CN bonds, and II'5! It is obtained by using a composite containing a compound with sufficient electron affinity to oxidize + as a carrier, and supporting titanium chloride with a valence of 1 or 2 on the carrier. As a carrier/-magnesium chloride, especially magnesium chloride and C-O or C-N
A method in which a compound containing a bond and a compound having sufficient electron affinity to oxidize +p i 2+ are co-pulverized, or organomagnesium is co-pulverized using an appropriate chlorogenating agent.・When making magnesium rogenide, e
Compounds containing -O or C-N bonds and Tl112+
A method of obtaining magnesium halide in the presence of a compound having sufficient electron affinity to oxidize it, or using a suitable precipitating agent with magnesium halide dissolved in an appropriate solvent...When obtaining magnesium halide as a solid, C. -O or C
There is a method in which a compound containing a -N bond and a compound having sufficient electron affinity to oxidize Ill H2+ are present.

In these cases, it is also possible to coexist a solid compound such as S i O, At20s, etc. Titanium chloride with a valence of 1 or 2 is supported on the carrier obtained in this way.The supporting method is to simultaneously support the above-mentioned carrier during production, or to apply the obtained carrier to a titanium chloride solution or liquid chloride. It is also possible by dispersing it in titanium and contacting it.

In the present invention, examples of compounds containing a C-0 or C-N bond include alcohols, ethers, esters, amides, and amines.

Among them, carvone 1 year old ester, ether, Quir11 ester, and alkoxy silicon. Orthocarboxylic acid esters are preferably used, and L is preferably ethyl orthoacetate or ethyl benzoate.

In the present invention, an example of a compound having sufficient electron affinity to oxidize Ti"+ is a compound having a principal electron affinity of 27.6 eV15'-a Lmm or more of the ionization potential of Ti2+, where n is good; There is no particular gallop, and in some cases 27.6 e v/?-a tm
Even if the electron affinity is below, Ti''+ can be oxidized if an electron-donating compound that forms a complex with l'it+ is present.

Preferably Au", Ur3+, Fel", InB
+, Mn' +, )+5 +.

)'b4", SbS+, Si4", Sn4",
Salts such as V4”, WB”, Se3 +, etc. are used fl
, Preferred are chlorides, sulfates, and carbonates.

As the organometallic compound used in the present invention, a known Ziegler-Natsume catalyst is used, including B, Zn, and At.

Organometallic compounds such as Mf, Li, or their composites are used, especially AtCD.
J is preferably used. Specifically, diethylaluminum chloride, dipropylaluminium chloride, dibutylaluminum chloride, cyhexylaluminum chloride, triethylaluminum, tripropylaluminum, and tributylaluminium are used alone or as a mixture.

In the present invention, it is also possible to use a stereoregular agent in combination if necessary.T: Yes, for example (C ester).

Ethers, orthoesters, and orthotropic esters are preferably used.

Examples of the α-olefin to which the method of the present invention is applied include propylene, butene-1, hexene-1, etc. Among them, propylene and plan-1 are preferably used.

Although known methods may be used as the polymerization method in the method of the present invention, bulk polymerization and gas phase polymerization are particularly effective. Polymerization temperature is room temperature to 90℃1
The polymerization pressure is generally within the range of normal pressure to 50 kgZdG.

By applying the HJ method of the present invention, it is possible to obtain a poly-α-olefin with a high ethylene content under relatively low ethylene partial pressure conditions, which is of great industrial significance.

The present invention will be explained in more detail with reference to Examples below.

Example 1 Production of a four-assembly type transition metal catalyst A vibratory mill equipped with two grinding pots each having an internal volume of 600 m and containing 80 copper balls each having a diameter of 12 bars was used.

In this pot, 20 ha of magnesium chloride, 2 me of ethyl acetate, and 2 v of iron trichloride were added per piece under a nitrogen atmosphere, and the mixture was pulverized for 40 hours. 2x7. After adding 100 ml of titanium tetrachloride and stirring at 8°C for 2 hours, the supernatant liquid was removed by decantation. Next, a washing operation of stirring 200 ml of n-hebutane at processing room temperature for 15 minutes and removing the supernatant liquid by decantation was repeated seven times.

Next, 200 d of n-heptane was further added to prepare a carrier-type transition metal catalyst slurry. Take out a portion of this slurry and sample it and get '1゛! I measured 1g of supported transition metal catalyst? It contained 2.27 wt%.

(I3) Polymerization S [Jδ-
1.5 kg of propylene was charged into a No. 32 autoclave, then 2Nt of hydrogen was charged, and the V-3 temperature was increased to 5.
After the temperature was lowered to 0°C, ethylene was added at a partial pressure of 5 kgZ-〇. Then, after raising the same temperature to 45°C, 30q of the above carrier-type transition metal catalyst, 0.24-me of diethylaluminum chloride, 0.14me of methyl P-toluate, and 0.2011L of triethylaluminum were dispersed in 50.8-liter of 11-heptane. When the slurry was press-fitted, the temperature reached 50°C in about 30 seconds. Pressure to ethylene partial pressure 5 kg
/ ctlr (polymerize for 10 minutes while adding ethylene so that j.

Then add 50 rnl of methanol! After stopping the polymerization, the monomer from the bed reaction was purged, the polymer was taken out, dried at 60°C under reduced pressure, weighed to 11%, and then the ethylene content of the polymer was measured by C'NMR method. It is shown in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 2 Table 1 shows the results in the same manner as in Example 1, except that the additives shown in the table were changed to the 1-compounds shown in the table. It can be seen that the ethylene content of the copolymer with the added catalyst 't'' and f'1. is higher than that of the copolymer with no oxidizing agent added.

Claims (1)

[Claims] (Re) In a method of random and/or block copolymerization of α-olefin and ethylene, magnesium halide and a compound containing U, -(J or C-N bond, and TI2+ are oxidized. using a composite containing a compound having sufficient electron affinity to
A method for copolymerizing olefins, characterized by using a catalyst made of a metal compound. (2) Claim 1, wherein the magnesium halide is magnesium chloride. [Method described in JIj. (3) The method according to claim 1 or 2, wherein the α-olefin is propylene and/or butene-1. (4) The method according to claim 1 or 2, wherein the compound having sufficient electron affinity to oxidize Ti2+ is a metal salt.