JPS604507A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To polymerize an olefin in high activity and to suppress extremely formation of insoluble polymer as a by-product, by using a catalytic system consisting of a transition metal compound soluble in a hydrocarbon, a magnesium compound soluble in a hydrocarbon, an organoaluminum compound, and a specific electron donor. CONSTITUTION:An olefin is (co)polymerized in the presence of a catalyst consisting of (A) a transition metal compound (e.g., TiCl4, etc.) soluble in a hydrocarbon medium, (B) a magnesium compound (e.g., dialkyl magnesium, etc.) soluble in a hydrocarbon medium, (C) an organoaluminum compound (e.g., ethylaluminum sesquichloride, etc.), and (D) at least one of a silicon-containing compound (e.g., diphenylsilane, etc.) and a nitrogen-containing compound (e.g., 2,2,6,6-tetramethylpiperidine, etc.). EFFECT:A polymer having improved transparency, greasiness, and blocking properties is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the polymerization or co-production of 5-olefins in the presence of a catalyst formed from a transition metal compound soluble in a hydrocarbon medium, a soluble magnesium compound, an organoaluminum compound and a specific electron donor. The present invention relates to a polymerization method, and more particularly to a polymerization method that suppresses the formation of a polymer that is insoluble in a hydrocarbon medium (hereinafter sometimes abbreviated as an insoluble polymer) and has improved polymerization activity.

In the present invention, the term "polymerization" is used to include copolymerization, and similarly, the term "polymer" is used to include copolymers.

Many proposals are known regarding supported highly active transition metal compound components in which transition metal compounds are supported on various magnesium compounds. Usually, it is necessary to prepare the supported catalyst component prior to the polymerization of olefins. Furthermore, since the supported catalyst component is insoluble in the hydrocarbon solvent for polymerization,
Special care is required to achieve quantitative charging or uniform dispersion of the catalyst components into the polymerization vessel. Even if such considerations are taken, as long as the above-mentioned insoluble catalyst component is used, the resulting polymer will often be inhomogeneous.

In order to avoid the above-mentioned disadvantages, a method for highly active polymerization of olefins using a magnesium compound soluble in a polymerization solvent is disclosed in Japanese Patent Publication Nos. 46-15655 and 46-5196.
This method has been proposed in Japanese Patent Publication No. 8 and Japanese Patent Publication No. 5O-59H7. However, the degree of increase in yield brought about by using a magnesium compound in these proposals is within about 10 times compared to the case where no magnesium compound is used, and the above-mentioned supported catalyst with the above-mentioned disadvantages is It was hard to say that it was comparable to the ingredients. In particular, the above-mentioned Special Public Service Showa 50
-391i Publication No. 7 proposes a method of dissolving and using various magnesium compounds,
For example, regarding magnesium chloride, a method is disclosed in which it is used after being dissolved in an organoaluminum compound. However, it has been shown that the polyethylene yield increase achieved by using such magnesium compounds is at most just under 6 times (Example 27 of the proposal).
~60).

The present inventors have discovered that the previously proposed insoluble catalyst has a high activity that is at least superior to the high activity achieved by using a catalyst component that is insoluble in the hydrocarbon solvent for polymerization. Research was conducted to overcome the disadvantages mentioned above in the use of ingredients. As a result, by using a catalyst formed from a specific electron donor in addition to a soluble transition metal compound component, a soluble magnesium compound component, and an organoaluminum compound component in the hydrocarbon medium that is the polymerization solvent, the aforementioned prior art The present invention was achieved by discovering that the catalyst system has higher activity than conventional catalyst systems proposed in technical literature, and produces significantly less by-product of insoluble polymer during polymerization.

Accordingly, an object of the present invention is to provide a method for polymerizing olefins using a novel catalyst for olefin polymerization formed from components soluble in a hydrocarbon as a polymerization medium. Another object of the present invention is to provide a polymerization method with high activity during polymerization and with a low content of insoluble polymers. The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

To summarize the invention, the present invention comprises (N) a transition metal compound soluble in a hydrocarbon medium, (B)
Magnesium compounds soluble in hydrocarbon media, (0)
consisting of polymerizing or copolymerizing an olefin in the presence of a catalyst formed from an organoaluminum compound and (D) at least one electron donor selected from the group consisting of silicon-containing compounds and nitrogen-containing compounds. The gist of this paper is a method for polymerizing olefins.

The transition metal compound component of the catalyst component used in the method of the present invention (Shu is a transition metal compound component soluble in a hydrocarbon medium, and the transition metal compound is preferably a titanium compound or a vanadium compound, in particular a soluble titanium compound. A compound having the general formula % (wherein R represents a hydrocarbon group, X represents a halogen,
It is a tetravalent titanium compound represented by Ti (354, TiBr4, T
i engineering. , Ti(OOH5nCe5, T1(002H5
) Ce3, T l (OO6H5) Ce 5, T i (
002H5) 2012, Ti (005H7) 20g2,
Ti(0(!2H5)30e, Ti(OC6H5)
sc e, T1(OC2H5)4, Ti(o 05H7
)4, Ti(OC4H9)4, T1(OC6H43)4
, Ti(OC6H11)a, Tl(0(!5H17).

, Ti(OCH3(02H5)OHO4H9)4. T
i(009H,9)4, Ti(OC6H5(OH3)2
')4, T l (OCHz, )2 (OC4H9n2,
T l(005H7)s (o C4H9), Ti(O
C2H5)2(OC4H9)2, Ti(0(!2H40
e) 4, Ti(OC2II4oCH5)4, and the like.

In addition, as the soluble titanium compound component, any low-valent titanium compound such as trivalent or divalent titanium compound that is soluble in hydrocarbons or a titanium compound that has been subjected to solubilization treatment can be used. Yes, the crystal system does not matter.

Specifically, as such a soluble low-valent titanium compound component, 'ri', which is titanium tetrachloride reduced with titanium metal, is used.
cg3・T type, T i O reduced with aluminum metal
l 5・A type, hydrogen-reduced TiC/3-H type, (0
2H5)3A6, (c2H5)2A eo 7? ,(0
2H5) tsA e O7? t5(i'l J: Ti(QC!H3)3, Ti(QC!H3)3, Ti(
QC! 2H5)3, rt(oa4H9)6, rl(oa
n3)aj)2.20H30H5Ti(OCH3)20
6-OH,, alkoxytitanium compounds such as OH,
Examples include TiO472 obtained by hydrogen reduction of T1Ca5.

Normally solid transition metal compounds such as titanium dichloride and titanium dichloride are treated to become liquid before use. The treatment involves adding an oxygen-containing or nitrogen-containing electron donor such as, for example, an alcohol, ether, ester, amine, ketone, aldehyde, carboxylic acid, etc., preferably from about 1 to about 24 moles per mole of transition metal compound. Preferably, about 3 to about 15 moles may be brought into contact. In some cases, only a portion of the transition metal compound is dissolved, and in that case, it is preferable to decompose and use only the solubilized portion.

In addition, as a soluble vanadium compound, a compound represented by the general formula (%) is generally used, for example, voc43
, vo (o 02H5) a 122, vo (o
C! 2 H5) 3, VO (002H5) 1.504
+5,■0(OC4H9)3,vO[0CH2(CH2
)5CHC4H9]3, Va, 54, etc. can be exemplified. Furthermore, a low valence (2) compound which is insoluble in a hydrocarbon medium can also be used by solubilizing it with an electron donor in the same way as the low valence compounds mentioned above. For example, trihalogenated vanadium, which the present inventors have already proposed in Japanese Patent Application No. 58-1776, can be used.

The magnesium compound component (B) of the catalyst component used in the process of the invention is a magnesium compound soluble in the hydrocarbon medium. The hydrocarbon-soluble magnesium compound (B) is an organic or inorganic compound, and of course those that are hydrocarbon-soluble themselves can be used, but even if they are insoluble in hydrocarbons, they may be alcohols, carboxylic acids, aldehydes, It is also possible to use those made hydrocarbon soluble by using an electron donor such as ether or amine in combination. For example, dialkylmagnesium, diarylmagnesium, alkylmagnesium halide,
Examples include arylmagnesium halides, alkylmagnesium alkoxides, dialkoxymagnesiums, alkoxymagnesium halides, magnesium carboxylates, magnesium halides, and complexes of alkylmagnesium and alkylaluminum. More specifically, diisobutylmagnesium, dialkylmagnesium such as dew-octylmagnesium, diarylmagnesium such as diphenylmagnesium, n
- alkylmagnesium halides such as butylmagnesium chloride, isodecylmagnesium, arylmagnesium halides such as phenylmagnesium chloride, alkylmagnesium alkoxides such as n-butylmagnesium isopropoxide, isobutylmagnesium-2-ethyl-hexoxide, di-n - alkoxymagnesium halides such as nasialkoxymagnesium, 2-ethyl-hexoxymagnesium chloride, oleyloxymagnesium chloride, such as octoxymagnesium, judodecyloxymagnesium;
Magnesium carboxylates such as magnesium stearate, magnesium oleate, magnesium chloride,
Examples include magnesium halides such as magnesium bromide.

Among these magnesium compounds, those which are insoluble in hydrocarbons can be made soluble in hydrocarbons by using an electron donor. Suitable electron donors that can be used for this purpose are compounds containing oxygen or nitrogen atoms, such as alcohols, carboxylic acids, aldehydes, nif/lz, amines, and the like. Contact with the electron donor is preferably carried out in a hydrocarbon medium, usually at a temperature of about 65°C or higher, preferably about 80 to about 600°C.
More preferably about 1 at a temperature of about 100 to about 200°C.
This is carried out by contacting for about 5 minutes to about 5 hours, more preferably about 30 minutes to about 2 hours. The treatment under these conditions may be carried out in the coexistence of a transition metal compound insoluble in the hydrocarbon, and a method may be adopted in which both are dissolved together. Among these electron donors, those having about 6 to 20 carbon atoms are most preferred.

More specifically, nihexanol, n-octatool,
Aliphatic alcohols such as 2-ethylhexanol, n-decanol, n-tetradecyl alcohol, oleyl alcohol, alicyclic alcohols such as cyclohexanol, methylcyclohexanol, benzyl alcohol,
Aromatic alcohols such as methylbenzyl alcohol and isopropylbenzyl alcohol, aliphatic alcohols containing alkoxyl groups such as n-butyl cellosolve and 1-butoxy-2-propanol, caprylic acid, 2-ethylhexanoic acid, nonylic acid, capric acid , undecylenic acid,
Carboxylic acids such as oleic acid, caprylic aldehyde, 2
- Aldehydes such as edylhexyl aldehyde, decyl aldehyde, undecyl aldehyde, di-n-hexyl ether, di-n-octyl ether, di-n-decyl ether, di-n-)lysosyl ether, hexyl octyl ether, bis( Examples include ethers such as 1-octenyl)ether and bis(benzyl)ether, and amines such as heptylamine, octylamine, nonylamine, decylamine, laurylamine, undecylamine, and 2-ethylhexylamine.

In the present invention, various halogenating agents, preferably chlorinating agents, may be used together with the hydrocarbon-soluble magnesium compound. For example, halides of silicon, aluminum, etc., alkyl halides, hydrogen halides, etc. can be shown.

As the organoaluminum compound component (0) used as a catalyst component in the method of the present invention, compounds having at least one hl-carbon bond in the molecule can be used, and examples include the following types of compounds: can.

(1) General formula (R) mAl(OR) HpXq (where R1 and R2 are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other. is halogen, m is 0≦m<3
, n is 0≦n<3, p is 0≦p<6, q is a number of 0≦q<3, and m ten n f p+q=6)
an organoaluminum compound represented by (11) a complex alkyl of a Group 1 metal and aluminum represented by the general formula MAl(R)4 (where M is Ll, Na or K, and R is the same as above); Examples include chemical substances.

Examples of organoaluminum compounds belonging to 1) above include the following.

General formula (R)mA/(oR), .

(Here, R1 and R2 are the same as above. m is preferably a number of 1.5≦m<1.) An organoaluminum compound represented by the general formula (R1)mA"3-m (wherein R1 is the same as above.X represents halogen, m
is preferably an organoaluminum compound represented by the formula (R1)mAIH3-m, where 0<m<3, where R1 is the same as above, and m is preferably 2≦m<
3) represented by the general formula (R)m/1(OR)nXq (where R and R are the same as above. X represents a halogen, and 0<m≦3.0≦n <3.0≦q black and m+n+q=3), etc. can be exemplified.

Among the aluminum compounds belonging to the above (1), more specifically, trialkylaluminums such as triethylaluminum and tributylaluminium, trialkenylaluminums such as triisoprenylaluminum, dialkylaluminums such as diethylaluminum ethoxide, diethylaluminum ethoxide, etc. In addition to alkoxides, alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide, general formula (R1)2.5Al(OR2). Partially alkoxylated alkylaluminum, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminium bromide, "dialkylaluminum hydride, ethylaluminum sesquichloride, butylaluminum sesquichloride," having an average composition represented by , 5, etc. Partially halogenated alkyl aluminum sesquihalogenides such as ethyl aluminum sesquipromide, alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc., diethyl aluminum Aluminum hydride, dialkyl aluminum hydride such as diptylaluminum hydride, partially hydrogenated alkyl aluminum such as ethyl aluminum dihydride, alkyl aluminum dihydride such as probyl aluminum dihydride, ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride , partially alkoxylated and halogenated alkylaluminiums, such as ethylaluminum ethoxypromide. Moreover, as a compound similar to (1), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. Examples of such compounds include (C2H5)2AlOAl(C2H5)2
, (C4H9)2AβotJjcO4Hc))2,
These exemplified compounds may be used in combination.

Compounds belonging to the above (C2H5
)4, LlAl(C7H1,)4, and the like. Among these, it is particularly preferable to use trialkylaluminium and alkyl aluminium halide.

Further, the electron donor (D) component used as a catalyst component in the method of the present invention is at least one compound selected from the group consisting of silicon-containing compounds and nitrogen-containing compounds.

The silicon-containing compound includes a 5i-0-0 bond, a 5i-
Compounds having an H bond or a 5i-N-G bond are preferably used. The organosilicon compound catalyst component (c) having a 5i-0-0 bond is, for example, an alkoxysilane or an aryloxysilane. As an example of this, the general formula Rn5i(OR3) -n (wherein 0≦n≦4, R is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group) etc., or represents a halogen or hydrogen, and R3 is a hydrocarbon group, such as an alkyl group,
Examples include silicon compounds represented by cycloalkyl groups, aryl groups, alkenyl groups, alkoxyalkyl groups, etc. (provided that n R1 (4''-n) OR6 groups may be the same or different). .Also, as another example, O
Examples include cyclohexanes having an R group and silyl esters of carboxylic acids. Other examples include compounds in which two or more silicon atoms are bonded to each other via oxygen or nitrogen atoms.

More specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyljethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane , phenyltrimethoxysilane, r-chloroprohyletrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, diphenylsilane, γ-aminopropyltriethoxysilane , chlortriethoxysilane, ethyltriisopropoxysilane,
Vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryl-oxysilane, vinyltris(β)
-methoxyethoxy)silane, vinyltriacetoxysilane, diethyltetraethoxydisiloxane, phenyldiethoxydiethylaminosilane, and the like. Among these, particularly preferred are methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
These include vinyltributoxysilane, diphenylsilane, etynopediphenyldimethoxysilane silicate, diphenyljethoxysilane, methylphenylmethoxysilane, and the like represented by the formula Rn S i (OR5) 4-U.

Specifically, the compound having the 5i-N-0 bond is:
Phenyldiethoxydiethylamide/silane, diethylaminotrimethylsilane, piperidinotrimethylsilane,
Examples include tetrakis(dimethylamino)silane, methyltripipezinosilane, and 1-trimethylsilylpyrrolidine.

Furthermore, sterically hindered amines are preferably used as the nitrogen-containing compound. Specifically, the sterically hindered amine has the general formula (wherein R4 is a hydrocarbon group, preferably a substituted or unsubstituted alkylene group, and preferably the alkylene group has 2 or more carbon atoms. .

In the case of a substituted alkylene group, the substituent is, for example, a hydrocarbon group such as an alkyl group, an acyloxyl group, an alkoxyl group, and the like. R, R, R+R are hydrogen or a hydrocarbon group which may have a substituent, at least one of R5 and R6 and at least one of R5 and R6 is a hydrocarbon group, and R5 and R1 'or R7 and R
8 may be connected to each other to form a ring, for example a carbocycle or a heterocycle. Preferably, all of R5, R6, R7, and R8 are hydrocarbon groups. In addition, when one of R5 and R6 and/or R7 and R8 is hydrogen, the other is preferably a secondary or 6th class hydrocarbon group. , R, R, R, and R are hydrocarbon groups that may have a substituent, and R9 and R10 or R11 and R12 may each form a ring.Also, with either R9 and R10,
Either R11 or R12 may be connected to form a ring. R13 is a substituted methylene diamine compound having a skeleton represented by hydrogen or a hydrocarbon group.

Specifically, for example, the heterocyclic compound may have the general formula (wherein R5, RA, R', R8 are the same as above, R14
is hydrogen or a substituent such as a hydrocarbon group, metal, or alkyl metal; R15 is hydrogen or a hydrocarbon group such as an alkyl group, an acyloxyl group, or an alkoxyl group; O≦n≦6.0≦
m≦2, and n or m R15s may be the same or different. ) can be exemplified as a compound having the following skeleton.

More specifically, 2,6-substituted piperidines such as these and 2,5-substituted pyrrolidines such as these can be exemplified.

Further, the substituted methylene diamine compound is specifically N, N, N', N'-tetramethylmethylene diamine, N, N, N', N'-tetraethyl methylene diamine, 1,3-dibenzylimidazolidine , 1,6-dipenzyl-2-phenylimidazolidine, and the like.

In the method of the present invention, the olefin compounds used for polymerization are ethylene, propylene, 1-butene, 4-methyl-
These include 1-pentene and 1-octene, and these can be subjected to not only homopolymerization but also random copolymerization and block copolymerization. In copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can be selected as copolymerization components. polyunsaturated compounds such as butadiene, isoprene, 1°4-hexadiene, dicyclopentadiene,
When copolymerizing 5-ethylidene-2-norbornene, 1,7-octadiene, etc., 0.1 to 10 mol%,
Preferably, the copolymerization may be carried out in a proportion of about 0.2 to 5 mol%. In this case, the resulting copolymer has an iodine value of about 5 to 50, and can be vulcanized with sulfur. Its vulcanized properties are also excellent, and it can be used as a vulcanized rubber with high strength. The resulting polyolefin may be resin-like or rubber-like.

The method of the present invention is characterized in that the polymerization activity of the catalyst is significantly improved compared to conventional olefin polymerization systems using titanium-based catalysts composed of various soluble catalyst components. Furthermore, according to the method of the present invention, compared to conventional olefin polymerization systems using titanium-based catalysts consisting of various soluble catalyst components, the by-product of insoluble polymers is significantly less, and polymers or polymers with excellent uniformity can be produced. It has the characteristic that a polymer can be obtained.

Furthermore, according to the method of the present invention, alcohol, carboxylic acid, aldehyde, ether, amine, etc. can be added to a hydrocarbon-insoluble magnesium compound such as magnesium halide as a soluble magnesium compound component among the catalyst components. In addition to the above-mentioned characteristics, the use of soluble magnesium compounds formed by the action of oxygen or nitrogen-containing electron donors results in a narrow molecular weight distribution of the resulting polymer or copolymer, especially for low molecular weight, low density polymers. Since the content of coagulants is significantly reduced, a polymer with improved transparency, stickiness and blocking properties can be obtained. For example, polyolefins with good transparency can be produced by copolymerizing ethylene with other α-olefins or propylene with other α-olefins. Compared to polymers obtained from supported catalysts that are insoluble in hydrocarbon solvents, they have the advantage of being much superior in transparency and having very little stickiness, which impairs commercialability.

In the present invention, polymerization is carried out in a hydrocarbon liquid medium using the above catalyst components. Examples of the hydrocarbon liquid medium include aliphatic hydrocarbons and their halogen derivatives such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclohexane, methylcyclopentane, and methylcyclopentane; Examples include halogen derivatives thereof; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogen derivatives thereof such as chlorobenzene. Moreover, the olefin itself used for polymerization can also be used as a liquid medium.

In the method of the present invention, the proportions of each catalyst component used are as follows. The amount of the soluble transition metal compound component (A) used is preferably about 0.00 in molar ratio of the soluble transition metal compound component/soluble magnesium compound component (E).
5 to 1, more preferably about 0.01 to about 0.3
3. Zara more preferably about 0.033 to about 0.062
It is in the range of 5. In addition, the concentration of the transition metal compound per liquid phase 11 is preferably about 0.000 in terms of transition metal.
5 to about 1 milligram atom, more preferably about 0.0
1 to about 0.5 milligram atoms, and the concentration of the soluble magnesium compound component (B) is preferably about 0.0005 to about 200 milligram atoms in terms of magnesium atoms.
milligram atoms, more preferably about 0. It is best chosen to have an OD of 3 to about 50 milligram atoms. On the other hand, the organoaluminum compound <O) must be added at least in an amount that will not be deactivated by alcohol or the like, and usually about 5 to about 2000 gram atoms, preferably about 2 aluminum atoms per 1 gram atom of the transition metal.
Preferably, 0 to about 500 gram atoms are used. Furthermore, the usage ratio of the electron donor component (D) is:
Usually about 0.01 to about 1 gram atom, preferably about 0.05 to about 0.8 gram atom of silicon or nitrogen atom in the electron donor component per gram atom of aluminum in the organoaluminum compound component. range.

In the present invention, although the polymerization method is arbitrary, it is also possible to adopt a continuous polymerization method in which olefins are continuously supplied to the polymerization system and a hydrocarbon solution containing the polymer is continuously discharged from the polymerization system. However, a semi-continuous method or a batch method can also be adopted.

In the method of the present invention, each of the catalyst components (A) (B) (
C! > (D) may be separately supplied to the polymerization system, or optional components thereof may be premixed in advance. For example, (A) and (B), (B) and (0), (
0) and (D) may be premixed and used. Alternatively, a mixture consisting of a hydrocarbon-insoluble transition metal compound and a magnesium compound may be brought into contact with the electron donor to simultaneously solubilize them.

In the process of the invention, the temperature during the polymerization or copolymerization of the olefin is generally from 20 to about 300°C, preferably from about 65 to about 200°C.

In particular, in order to produce a polyolefin with good transparency in the copolymer production method, it is preferable to perform liquid phase polymerization using an inert hydrocarbon medium and select a temperature at which the polyolefin dissolves. For example, ethylene and a small proportion of other α-
When a resinous copolymer is produced by copolymerization with an olefin, the temperature is preferably from the melting point of the copolymer to about 200°C. The polymerization pressure is preferably from atmospheric pressure to about 10 Dkq/cm -a, particularly from atmospheric pressure to about 50 kq/C1n -G.

In carrying out the present invention, hydrogen, organometallic compounds of Group 2 metals of the periodic table, and/or various electron donors other than those mentioned above, such as alcohols, ethers, and esters, are used for the purpose of controlling molecular weight, stereoregularity, etc. , amines, ketones, carboxylic acids, amides, phosphorus compounds, sulfur compounds, acid anhydrides, etc. may also be present.

Next, a more detailed explanation will be given with reference to Examples.

Example 1 Eleven sufficiently dried separable flasks were equipped with a stirring blade, a gas blowing tube, a thermometer, a condenser, and a dropping funnel, and were sufficiently purged with nitrogen. N-decane 25QJ, which had been dehydrated and dried using a molecular sieve, was placed in this flask. Under nitrogen flow, add 0.00 TlC14 to the dropping funnel in terms of T1.
625mMCD, 025mM/l) and added ethylaluminum sesquichloride 0.1875mM, diphenylsilane (SIH2(c6H5-2) [1
,01875mM was added. 9 on/hr of dry ethylene through a gas blow tube.

A mixed gas of propylene 210 (J/hr) was passed through a flask whose temperature was controlled at 70°C for 10 minutes.

”-C6H43)2Mg is 0.0625mM in terms of Mg.
Copolymerization was initiated by adding T 10 (J 4) dropwise into the flask and polymerization was carried out at 70″C for 30 minutes. Copolymerization was stopped by adding 10 mn of butyl alcohol to the polymerization solution. .The solution during copolymerization is homogeneous;
No formation of insoluble polymer was observed. After the polymerization, the polymerization solution was poured into a large amount of amethane and methanol mixture to obtain a copolymer. The yield of the copolymer was 11.3 g, and the ethylene (hereinafter sometimes abbreviated as 02') composition in the copolymer was 59.3 mo1%.
Intrinsic viscosity (hereinafter, [η]) measured in decalin at 35°C
It is sometimes abbreviated as. ] was 2.11617 g.

Comparative Example 1 In Example 1, diphenylsilane was not used (TiCl2, ethylaluminum sesquichloride,
(n C!6H1spMg usage amount 0.01 each
25mM, 0.375mM, 0.125mM, and the flow rates of ethylene and propylene were changed to 1201mM, respectively.
When the same procedure as in Example 1 was carried out except that the copolymerization rate was changed to 1801/hr and 1801/hr, the formation of an insoluble polymer was observed during copolymerization. The yield of the copolymer was 15.3 g, the ethylene composition was 61.2 mo1%, and [η] was 1.95
It was a#/g.

Examples 2 to 8 The same procedure as in Example 1 was carried out, except that the compounds shown in Table 1 were used instead of diphenylsilane, and the results shown in Table 1 were obtained.

Example 9 In the copolymerization of Example 1, (n O6H13) 2'
The same procedure as in Example 1 was conducted except that n-04Hn-04H91i1 was used instead of Mg. The yield of copolymer is 11.0g, and its 02″ composition is 60.1mol%
and [η] was 2.32 dβ/g.

Example 10 Example 1 except that in Example 1, instead of “-C6H13)2Mg, na4H9Mgcn was used and 0.375mM of ethylaluminum sesquichloride was used.
I did the same thing. In addition, n −04H9M g O(l
is 6 of n Oi, HqMgOl in n-decane solvent.
Double the molar amount of 2-ethylhexanol (hereinafter sometimes abbreviated as EHA) was added and stirred for 1 hour at 130°C to obtain a homogeneous solution, which was then used for polymerization. The yield of the copolymer was 10.6, its 02'' composition was 61.0 mo1%, and [η] was 2.45 d1/g.

Example 11 The same procedure as in Example 10 was carried out except that the Mg compound in Example 10 was changed to (C2H50)MgCl. In addition, (C2H5SMgC1 is 5 times mole of EH as (C2H50)MgCβ in n-decane solvent.
K was added thereto, and the mixture was stirred at room temperature for 1 hour to obtain a homogeneous solution. The yield of copolymer was 10.2 g, of which 02
"The composition is 60.5 mo1%, and [η] is 2.51
d (1/g.

Example 12 In Example 1, the Mg compound was dissolved in a homogeneous solution of magnesium stearate in n-decane (in n-decane solvent,
Example 1
I did the same thing. The yield of the copolymer was 10.7 g, its 02″ composition was 60.1 mo1%, and [η]
was 2.35617g.

Example 13 In Example 1, instead of (n-C6H1!,)2Mg, a complex of di-n-butylmagnesium and triethylaluminum was used to prepare Al7.5(n (!4H9)2M
The same procedure as in Example 1 was conducted except that g.(C2H5)3A was used. The yield of copolymer is 11. ;l! g, its a i /composition was 60.7 ma1%, and [η] was 21.56717 g.

Example 14 Example 1 except that ethylaluminum sesquichloride was added to the polymerization flask, and diphenylsilane and (na6n13)2Mg-Tic (14) were added in this order at the start of polymerization to perform polymerization. The procedure was carried out in the same manner as in 1. The yield of copolymer was 10.7 g, and 0.
2' composition is 60.4 mo1%, [η] is 2.0
5d (4/g).

Example 15 The same procedure as in Example 1 was carried out, except that in Example 1, diethylaluminum sesquichloride and (n cbHls) 2Mg were added to the polymerization flask, and diphenylsilane was added at the beginning of the M interval. . The yield of the copolymer was 10.8 g, and the 02' composition of 5 was 60
．． 7 mo1%, and [η] was 2.13 dl/g.

Example 16 In the copolymerization of Example 1, 0.25 g of 5-ethylidene-2-norbornene and T i C! 140.01
Add 25 mM to the addition funnel, and add 0 each of ethylaluminum sesquichloride and diphenylsilane.
．． Change to add 375mM, 0.0375mM to the flask, add (n-06H15)2Mg to 0.125mM
The same procedure as in Example 1 was carried out except that M was added.

The solution during copolymerization was homogeneous, and no insoluble polymer was observed to form during copolymerization. The yield of copolymer is 16.3g
and its 02″ composition is 62j mo1%, [
η] was 1.55, and the iodine value was 5.6.

Example 17 The same procedure as in Example 16 was carried out except that 5-ethylidene-2-norbornene was changed to dicyclopentadiene. The yield of the copolymer was 14.5 g, its 02' composition was 66.5 mo1%, and [η] was 1.
74 aff/g, and the iodine value was 5.8.

Example 18 (1) Catalyst synthesis A thermometer, nitrogen injection tube, dropping funnel, and injection funnel cooling tube were attached to a sufficiently dried 200 mJLI four-bottle round bottom flask, the air was sufficiently purged with nitrogen, and Ti was added to the round bottom flask.
C13 (manufactured by Toho Titanium Co., Ltd., product name TAO151)
5. [Add lrnM and 50 ml of n-decane, and then add E
45mM of HA was added and stirred at 80°C for 1 hour to obtain a blue-green homogeneous solution.

(It) In Copolymerization Example 1, the above (T of D) was used instead of TlC14.
1a The same procedure as in Example 1 was carried out except that AX3 solubilized was used. The yield of the copolymer was 11.0 g, its 02″ composition was 60.2 mo1%, and [η]
was 2.10 d12/g.

Example 19 The catalyst synthesis of Example 18 was carried out in the same manner as in Example 18 except that 50 mM of undecylenic acid was used instead of EH'A. The yield of copolymer is 10.1
g, its 02' composition is 61.0 mo1%,
[η] was 2.14 an/g0 Example 20 In Example 1, T ia (T i
Except for changing to use (OB u ) 4,
The same procedure as in Example 1 was carried out. The yield of copolymer is 10.4
g, and its C2/composition was 60.8 mol % teal, [η] 2.14 dβ/g.

Example 21 In Example 1, VOa#3 was used instead of T1C14, and ■0C16, diethylaluminium sesquichloride, (n C6H13)2Mg.

The amount of diphenylsilane used was 0.05 mM each.
.

1, OmM, 0.5mM, and 0.1mM, and the copolymerization was performed in the same manner as in Example 1, except that the copolymerization was performed at 30°C. The yield of copolymer was 4.8 g, of which 0
The 2' composition is 58.5 mo1%, and [η] is 3.5
It was 4d, 5/g.

Comparative Example 2 The same procedure as in Example 21 was carried out except that diphenylsilane was not used. The yield of copolymer was 3.0 g, and its 02' composition was 59.6
The mole content was 1%, and [η] was 3.94 al/g.

Example 22 (1) Preparation of hydrocarbon-soluble MgCβ2 50 g of commercially available anhydrous magnesium chloride was mixed with n-decane 14 in a nitrogen atmosphere.
205 g of EHA (6 times the mole relative to magnesium chloride) was added, and the temperature was gradually raised while stirring.
The reaction was carried out at 160°C for 1 hour. The solid disappears completely;
A colorless and transparent liquid was obtained. Even when this solution was cooled to room temperature, no solid was precipitated, and the solution remained clear and colorless.

Thus, a solubilized magnesium chloride-2-ethylhexyl alcohol complex was obtained (hereinafter referred to as Mg liquid).

(1) Polymerization was carried out in the same manner as in Example 1 except that the above Mg solution was used instead of (nCbHl2Mg) and dimethyljethoxysilane was used instead of diphenylsilane. However, the treatment after completion of polymerization is (
I did it using the method described in IID. The yield of copolymer is 9.
5g, its 02″ composition was 61.8m01%, [η] was 2.53J/g, and the low molecular weight content was 0.70%.

The content of low molecular weight substances was determined by the method described in (2) below.

GOD Method for measuring the content of low molecular weight substances in copolymers After polymerization, the polymer solution was mixed with 500 mn of acetone and 50 mn of methanol.
Electric mixer with m1 added (National MX150S
) and stir to precipitate the copolymer and at the same time dissolve the low molecular weight substance into the acetone solution. After curing the precipitated polymer, it is dried under reduced pressure and the yield of copolymer is calculated. For filtration, the catalyst residue is extracted into the hydrochloric acid water by shaking it with hydrochloric acid water (distilled water 3 DOm/, 36 wt% hydrochloric acid 2 mβ) in a separating funnel, and then the na layer is collected. Furthermore, the weight of the low molecular weight product obtained by removing n −01° is defined as the yield of the low molecular weight product. The low molecular weight substance content was determined by the following formula G.

Comparative Example 6 The same procedure as Example 22 was carried out except that dimethylethoxysilane was not used. The yield of the copolymer was 4.0 g, and its C" composition was 64.
Omo was 1%, [η] was 2.94 an/g, and the low molecular weight matrix content was 1.5%.

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi

Claims (1)

[Scope of Claims] (A) A transition metal compound soluble in a hydrocarbon medium, (E) A magnesium compound soluble in a hydrocarbon medium, (0) An organoaluminum compound, and CD) A silicon-containing compound and a nitrogen-containing compound A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of a catalyst formed from at least one electron donor selected from the group consisting of: