JPS619406A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a polyolefin having high reactivity, high stereoregularity and a wide MW distribution, by polymerizing an olefin by using a catalyst comprising a titanium compound, an organoaluminum compound and an unsaturated ether compound. CONSTITUTION:An olefin is polymerized by using a catalyst comprising a titanium compound, an organoaluminum compound, and an unsaturated ether compound of the formula: R-O-R' (wherein R and R' are each a 1-20C hydrocarbon group, and at least one of these groups is a 4-20C unsaturated hydrocarbon group). Examples of the titanium compounds used include TiCl4, (C2H5O)4Ti, TiBr3 and TiI2. Examples of the organoaluminum compounds include trimethylaluminum and diethylaluminum dichloride. Examples of the unsaturated ether compounds include ethyl crotyl ether and 4-methoxy-1-butyne.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing olefins, which is characterized by using a catalyst comprising a titanium compound, an organoaluminium compound, and an unsaturated ether compound.

Generally, when producing molded products such as bottles, tubes, films, and sheets by extrusion molding or blow molding, it is important to select a polyolefin as a raw material that satisfies both mechanical strength and melt fluidity. However, polyolefins produced using conventional methods have a high molecular weight (if
There was a problem in that the mechanical strength improved but the fluidity decreased, and conversely, if the molecular weight was lowered, the fluidity improved but the mechanical strength decreased. As a way to solve these five problems, by widening the molecular weight distribution, mechanical strength and dissolved P
Various methods for producing polyolefins have been studied in order to satisfy both the requirements of Mi fluidity.

Conventionally, many production methods have been proposed to obtain polyolefins with a wide molecular weight distribution. Methods of disproportionation of transition metal compounds, methods of supporting transition metal compounds on specific carriers, and methods of using limited cocatalysts such as organoaluminium compounds and third components are known. Many polyolefins have very low stereoregularity, insufficient polymerization activity, or unsatisfactory molecular weight distribution values, and the values of polymerization activity, stereoregularity, and molecular weight distribution are not the same. A satisfactory catalyst system has not yet been found.In addition, a method of mechanically blending high molecular weight and low molecular weight polymers obtained using conventional acid catalysts during processing and polymerization temperature during polymerization.

A multi-stage polymerization method has also been proposed in which high and low molecular weight polymers are produced in single or multiple polymerization tanks by changing the chain transfer agent concentration etc. to obtain a polymer with a wide molecular weight distribution. There is. However, these methods have not yet reached an industrially completed technology because the molecular weight distribution of the resulting polyolefin is not significantly broadened or extra polymerization equipment is required.

As a result of extensive research into a method for producing polyolefin with a wide molecular weight distribution that is industrially advantageous from the above viewpoint, the present inventors have found that by using a catalyst consisting of a titanium compound, an organoaluminium compound, and an unsaturated ether compound, an industrially advantageous method for producing polyolefin with a wide molecular weight distribution has been developed. From a specific point of view, it was discovered that a polyolefin with sufficiently high activity, high stereoregularity, and extremely wide molecular weight distribution could be obtained, and the present invention was achieved.

That is, the present invention is an olefin polymerization method characterized by using a catalyst comprising a titanium compound, an organoaluminium compound, and an unsaturated ether compound.

As the titanium compound used in the present invention, any known titanium compound can be used without any restriction. For example, TiCt4. TiB
r,,TiI,,CH,0TiCt,.

C,H,OT i C11I, C,H,OT I C
48, C, H, TiCt8°C6H, TiCt8. (C
, H, O), TiCt,.

(08H, O), Tic/! ,,l (C,H,),T
iCt,.

(C,H,O),TIC/,,CC,H,'),Ti
.

(C, H, O), TI, (C, H, O), TI.

Examples include tetravalent titanium compounds such as (CH8QC,H,O) and TI. Other examples of titanium compounds include Tict, TlBr3. Til,.

CH,T amount CtS,CH,0TiCt! ,C,H,0
TiCt,.

c,a,o’ricz,,c,H,’ricz,.

(C!H+tO), Tic/! ,,(08)1.0),
TiBr.

In addition to trivalent titanium compounds such as (C, H, O), TI, (C, Hg0) aTi, TlC1TlBr obtained by disproportionation reaction of trivalent titanium halogen compounds,
, TiI, etc. Bivalent tita! An example is the number p gun compound.

Further, titanium compounds supported on an inorganic or organic carrier or treated with an electron-donating compound to change the polymerization kinetic rate constant can also be used as the titanium compound of the present invention.

As an inorganic carrier supporting a titanium compound, M g
CZ s 1M I (OH) @ 1M110,C
aO.

Ca(OH)B, Zn(OH)@+Mr(OH),,M
nO.

M,FCON1Ct,,At,0. ．． 810. , TiO
.

There are many things that can be mentioned. As an organic carrier, a fine powder consisting of a homopolymer or a copolymer of two or more monomers using a radically polymerizable polymer such as styrene, divinylbenzene, 4-vinylpyridine, or methacrylic alcohol is generally used as the organic carrier. Although any shape of fine powder can be used, porous spherical fine powder is preferably used.

The supporting operation is generally K (1) If the titanium compound is liquid, it can be used as is, or if it is solid, it can be dissolved in an electron-donating compound such as tetrahydrofuran, pyridine, methanol, or ethanol to make a solution, or it can be made into a solution using an inorganic carrier. Room temperature to 500℃ in a crusher such as a ball mill or vibration mill,
(2) A method in which the liquid or solution titanium compound is crushed and mixed with an inorganic carrier and then supported by heating at room temperature to 500°C. (3) A method is mainly applied in which the liquid or solution titanium compound is mixed with an inorganic carrier or an organic carrier and then supported by heating at room temperature to 500°C.

In these supporting reactions, electron-donating compounds such as organic acid esters and amines, which will be exemplified later, can be used as reaction accelerators as needed.

Titanium compounds treated with electron-donating compounds can also be used in the present invention. Generally, 0,001 to 10 moles of an electron-donating compound are added to 1 mole of the titanium compound in an inert gas atmosphere, and the mixture is reacted with the titanium compound at room temperature in an inert solvent such as hexane or heptane. Complexes of electron-donating compounds can be obtained.

Examples of electron-donating compounds include furcol (general formula R-OH, R, and R' are furkyl groups).

Hydrocarbon groups such as allyl group and phenyl group (the same applies hereinafter), ether (R-0-R'), ester (RCOOR'),
Aldehyde (RCHO) Fatty acid (RCOOH), Ketone (RCOR'), Nitrile (RCN), 7 min
(RnNH8-n, n==ol 1,
213), incyanate (RNCO), 7zo compound (RN=N-R'), phosphine (RnPR'
IB n T n ni1 + 2 + 3 ) + phosphite (P(OR), ), phosphinite (RP
COR')B).

Thionidel (RSR', n=1.2).

n　　　　! -n Examples include thioflucol (R8H).

Specific examples of electron-donating compounds include the following. Alcohols include methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, cresol, xylenol, ethylphenol, naphthol, etc. Ethers include diethyl ether, dirope 1-pyl ether, di- n-butyl ether, di(isoamyl)
ether.

Di-n-pentyl ether, di-n-hexyl ether, di-n-octyl ether, diigo-#cutyl ether, ethylene chloride+col methyl ether, diphenyl ether, tetrahydrofuran, 7-ninol,
diphenyl ether, etc. Esters include ethyl acetate, butyl formate, and amyl acetate.

Vinyl butyrate, vinyl acetate, ethyl benzoate.

Propyl benzoate, dithyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, rR-2-ethylhexyl toluate,
Methyl anisate, ethyl 7nisate, propyl anisate,
Ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, stutyl naphthoate, 2-ethylhexyl naphthoate.

Examples include ethyl phenylacetate. As an aldehyde,
7 Cetaldehyde, benzaldehyde, etc., and fatty acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid,
Koha (acid.

Examples include acrylic acid, maleic acid, and benzoic acid. Methyl ethyl ketone is a ketone.

Examples include methyl in butyl ketone and benzophenone.

Nitriles include 77tonitrile, and amines include methyl7mine, diethyl7mine, tributylamine, triethanolamine, pyridine, and aniline.

Examples include dimethyl-7-niline. Examples of incyanates include phenyl isocyanate and tolyl incyanate, and examples of azo compounds include azobenzene. Examples of phosphine include ethylphosphine, triethylphosphine, and tri-n-butylphosphine.

Examples of phosphites include di-n-octylphosphine and tri-7enylphosphine. Phosphites include dimethyl phosphite, di-n-octyl phosphite, tri-n-methyl phosphite, and triphenyl phosphite. Phosphinites include , ethyldiethylphosphinite, ethyldibutylphosphinite, phenyldiphenylphosphinite, etc. Examples of thioethers include diethylthioether and diphenylthioether.

Examples of the thioalcohol include methylphenylthioetherphite and propylene sulfide, and examples of the thioalcohol include ethylthioalcohol, n-propylfurfur, and thiophenol.

The titanium compounds listed below can be used with appropriate treatment with a tetravalent titanium tzzogen compound in order to improve polymerization activity and stereoregularity.

Further, in the present invention, (B) an organoaluminum compound is used as a cocatalyst when the titanium compound described above is used for olefin polymerization. As such organoaluminum compounds, known ones can be used without any restrictions, and generally have the formula RAtX (wherein R is carbon n
sn is an alkyl group having 1 to 20 numbers, X is a halogen atom or a hydrogen atom, and n≦3).

Organoaluminum compounds are used. Specifically, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-2-methylpentylaluminium 1 cum, tri-n-octylaluminum, tri-n −
Tessyl aluminum, diethylaluminum chloride, di-n-propylaluminum chloride, diisobutyl aluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride,
Ethylaluminum dichloride, isomethylaluminum dichloride, diethylaluminum fluoride.

ethylaluminum pumite, diethylaluminum iodide, diethylaluminum hydride,
Diisobutylaluminum hydride, imprenylaluminum, diethylethoxyfluminicum, ethyljethoxyaluminum, ethylethoxyaluminum; rum chloride. ethyl ethoxyaluminum bromide,
Examples include ethyl ethoxyaluminum iodide.

These organoaluminum compounds are one type or two or more types)
- can also be used in combination.

The amount of the organoaluminum compound used is 11 to 200 times, preferably 3 to 100 times, the amount of the titanium compound.

Together with these, it improves polymerization activity and stereoregularity [
An electron-donating compound may be used during polymerization. The amount of the electron-donating compound added is 10 times or less, preferably 01 times or more and 3 times or less by mole, relative to the amount of the titanium compound used.

In the present invention, for the purpose of broadening the molecular weight distribution, as (C) an unsaturated ether compound, general formula R-0-R is used.
An unsaturated ether compound represented by ' (R, El, ' is a hydrocarbon group having J to 20 carbon atoms, and at least one of R and R' is an unsaturated hydrocarbon group having 4 to 20 carbon atoms) It is extremely important that you use it. When the unsaturated ether compound according to the present invention is added to the above-mentioned known catalyst system, the stereoregularity of the resulting polymer is hardly affected, and the distribution can be particularly broadened on the low molecular weight side. Although the reason for this is unknown, the present inventors have found that the unsaturated group coordinates to the active site while the m atoms of the unsaturated ether compound suitably coordinate with the titanium or aluminum atom near the active site. Considering the model, we infer that the process of coordination, insertion, and growth of active sites with this structure is slightly suppressed.

In the above formula, an unsaturated hydrocarbon group having 4 to 20 carbon atoms (R
, R') as a chemical model: -(CM, +nC
) f=cH, (n=2-18).

-CHCH=CHCH3, -CH=CHCH, CH8゜-CH=CH(-CH2-)nC)f8 (n=1~1
7).

-CH=CHCH3 -CH=C2CHCH3, -CH=CH-CH=CHC
H.

(>-(CH,-)nCH=CH, (n=0-12)
.

-CH=CH-(CHB-)nC(CH8) 8(n=
0-14).

0~5), -CH=CH(-Q''' (X=I\
rogen atom), -ca=c4Q), -CH=CHi8
0+-(CE mountain <subject n=2-18), 0. ◇gu), 0 engineering (X is)-rogen atom).

-GCH1+nC=CM (n=2-18).

-CE:C-(OH2-)n　8 -c=c@　, -c=cQcmiOH.

(CH8).

-CH=■=CHB, -CH=0-CH=CH,.

-CH=CH-0, -CH, -0, -CH=◎.

etc. are listed.

Furthermore, specific examples of unsaturated ether compounds include 4-methoxybutene-1,6-medoxyhexene-1
．． 8-methoxyoctene-1,10-methoxydecene-
1,15-methoxy pectadecene-1,18-methoxyoctadecene-1,4-ethoxybutene-1゜6-nitoxyhexene-1,8-ethoxyoctene-1,11-
Ethoxy-undecene-1, methyl methallyl ether,
Ethyl crotyl ether, phenyl crotyl ether,
4-methoxy-1-butene, 1-methoxy-2-octyne, 4-methoxystyrene, 3-methoxystyrene, 2
, 3-dihydrobyran, 1-methoxy-1,3-cyclohexadiene, 2゜3-dihydet= -3-methoxy-
4H-villain.

4-methoxystilbene, β-methoxystyrene, 4-
Phenoxystyrene, 4-(1-propenyl)pyrocatechol dimethyl ether, saph-rho, 7-netol, 4
-allylphenoxybenzene, l-methoxy-4-pentenyl-4-benzene, 4-1-butoxystyrene, cyclohexyl-4-propenylbenzyl ether and the like.

The amount of the unsaturated ether compound added is 0.1 times or more and 10 times or less by mole based on the titanium atoms charged. Preferably it is 0.5 times or more and 5 times or less by mole. The titanium compound, the organoaluminum compound, the electron-donating compound, and the unsaturated ether compound according to the present invention can be charged into the polymerization reactor in any order, but in general, the organoaluminum compound, the electron-donating compound, and the unsaturated Ether compounds and titanium compounds are charged in this order.

As the olefin polymerization method, any known method can be used without any restriction. For example, the polymerization temperature is in the range of -30 to 300°C, preferably room temperature to 80°C, and the polymerization pressure is not particularly limited, but is preferably 3 to 50 atm from an industrial standpoint.

The polymerization method can be continuous or batchwise. Also full can of C4~C8°.

Dichloroflucan e.g. propane, hexane.

Slurry polymerization using an inert hydrocarbon solvent such as heptane or cyclo/xane, or liquid phase polymerization or gas phase polymerization without a solvent is also possible.

The polymerization of olefins in the present invention is a general term for homopolymerization of olefins, copolymerization of olefins, or copolymerization of olefins and polyenes. Ethylene is an olefin that can be used for polymerization.

Examples include propylene, aigtene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3□-1-methyl-1-pentene, 1-octene, and l-decene. Examples of the polyene include zutadiene, imprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norpol-77ene, and methyl-1,4-heyasanene.

In the copolymerization of propylene/propylene, especially propylene
It is preferable to carry out the copolymerization so that the content is mol % or more.

By employing the polyolefin production method of the present invention as described above, it becomes possible to easily improve both the mechanical strength and melt fluidity properties of the resulting polyolefin.

Furthermore, the polymerization activity of the catalyst and the stereoregularity of the resulting polyolefin are sufficiently satisfactory. Therefore, the method of the present invention is an extremely useful method when implemented industrially.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not particularly limited by the following examples.

The properties of the obtained polymer were measured and determined by the following method.

+11 Melt Flow Inodex (MFI) 230
'C, load to 216, A8TM D-1238-57
According to T.

(21M, /Mn) is the ratio between the weight average molecular weight M and the number average molecular weight Jl, and was measured by the GPC method (gel permeation chromatography method). The n-hebutane extraction residue was used as the GPC measurement sample.

(3) Rockwell hardness: 23° C., ASl”MD-785-5111I: Yes.

(4) Fizotto impact strength According to JIS K7110.

(5111 is the value obtained by subjecting the obtained polymer to Nxhlet extraction with n-hebutane for 6 hours and dividing the extraction residue by the initial Jtlt, expressed as a percentage.

(6) Tensile strength (yield strength) measurement According to ASTM D63B-72.

Example 1 (Catalyst Preparation) After purging a 500 cc three-necked flask with argon, dry hebutane aoocc and 0.1 mot of titanium tetrachloride were added, and the solution was maintained at -10°C. Then, a solution consisting of 5 Q Cc of dry hebutane and 0.1 mol of diethylaluminum chloride was added dropwise over 2 hours.

After continuing stirring at the same temperature for 2 hours, heat treatment was performed at 65° C. for 1 hour. After thorough washing with dry hebutane 0.1
A hebutane slurry of mol of titanium trichloride was obtained.

Then add 0.1 mot of diisoamyl ether,
After stirring at 35° C. for 1 hour, the mixture was dried again and thoroughly washed with butane. 0.25 mol of titanium tetrachloride was added to this, and 6
After stirring at 0°C for 2 hours, the mixture was dried and thoroughly washed with butane.
A titanium trichloride/heptane slurry 100 (!e) with a concentration of 1 mmol/CC was obtained.

(Polymerization) After filling a 1 ton autoclave with high purity argon gas, 500 cc of dehydrated and purified n-hebutane was charged, and diethyl aluminum chloride 8. Om mol and n-hebutane slurry of titanium compound prepared by the above method. After charging 2.011 mot-71 atoms, 6-medoxyhexey-1], Qm mot and 60'C
k: The temperature was increased. After stirring for 30 minutes to ripen the catalyst, while leaving argon at atmospheric pressure in the gas phase of the autoclave, hydrogen was charged with O-33KP/ctllG, and then purpylene was charged to 3.33 Kfp/crAG, which caused immediate polymerization. was R#I. After that, the autoclave pressure was increased to 3.33 K9/cd while continuously feeding pylene gas.
Polymerization was carried out for 90 minutes while maintaining Gk. To stop polymerization, the gas in the system was purged, and 59 cc of isopropyl alcohol was injected. As a result, II is 97.0%, bills are 32,
60,000, M, / town got 8.7 bolipro birenwo. Active tta 51! -pp/l-TiC1゜・hr-atm
Met. The results are shown in Table 1.

Example 2 SUS made hole 40 in CMt # made in ttvs US made FN7)
Prepare 0cc, add 0.2 mot of magnesium chloride, 0.5 mol of ethyl benzoate, and titanium tetrachloride.
This pulverized mixture slurry and dry hebutane at 200 eC were charged into an argon-substituted aoocc flask, which was refluxed for 2 hours and thoroughly washed with dry hebutane. The obtained solid supported 30 degTi and 7 g of solid titanium.

Using the catalyst prepared above, triethylaluminum 8. is substituted for diethylaluminium chloride. OWL mo
Polypropylene was obtained by polymerizing propylene under the same polymerization conditions as in Example 1, except that 6.0 ηL mot of ethyl benzoate was added to improve stereoregularity. The results are shown in Table 1.

Example 3 The same procedure as in Example 1 was carried out except that 100 mmat of diethylaluminium chloride was used. The results are shown in Table 1.

゛゛　Examples 4 to 6 0.27W mat of rhomethoxyhexene-1.

The same procedure as in Example 1 was performed except that the amounts were changed to 6 mmot and 2 Qmmol. The results are shown in Table 1.

Example 7 The same procedure as in Example 1 was carried out except that 11-dodecenyl ethyl ether was used instead of lomethoxyhexene-1. The results are shown in Table 1.

Example 8 6-Medoxyhexene-1 1. Ommot.

Instead, 7 netol (411 formula CH80QCH-CHC
H8) using 6 mmol, diethyl aluminum chloride 8. Om mob instead of ethanol-denatured aluminum (chemical formula E+,, At(OE t ) o, s
Example 1 except that C1,,) 20 m mot was used.
I did the same thing. The results are shown in Table 1.

Example 9-1O p-z thyl anisate 0.2? nmoL, I Qmm
The same procedure as in Example 1 was conducted except that ol was charged after addition of diethylflujnium. The results are shown in Table 1.

Comparative Example 1 The same procedure as in Example 1 was carried out except that 6-medoxyhexene-1 used in Example 1 was not used.

The results are shown in Table 1. A GPC chart of the polymer is shown in FIG.

Comparative Example 2 The same procedure as in Example 2 was carried out except that 6-medoxyhexene-1 used in Example 2 was not used.

The results are shown in Table 1.

Comparative Example 3 Table 1 shows the results of the same procedure as in Example 1 except that 40 m mat of 6-medoxyhexene-1 was used.

Comparative Example 4 The same procedure as in Example 1 was carried out except that 6-medoxyhexane was used instead of 6-medoxyhexene-1. The results are shown in Table 1.

Claims (1)

[Claims] (1) (A) Titanium compound, (B) Organoaluminium compound, (C) General formula R-O-R^1 (R and R^1 have 1 to 1 carbon atoms)
20 hydrocarbon groups, and at least one of R and R^1 is an unsaturated hydrocarbon group having 4 to 20 carbon atoms. A method for producing a polyolefin characterized by: