JPS5938211A - Polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain a highly stereoregular poly-alpha-olefin in high yields, by polymerizing an alpha-olefin with the aid of a catalyst comprising a specified activated titanium catalyst component and an organometallic compound. CONSTITUTION:A magnesium dialkoxide of formula I (wherein R<1> is a 1-20C alkyl, cycloalkyl or aryl group, or the like), e.g., magnesium dimethoxide, is reacted with an alcohol. Then, the treated magnesium dialkoxide is reacted with a halogen-containing titanium compound (e.g., TiCl4) of formula II (wherein R<2> is a 1-10C alkyl, cycloalkyl or aryl group, or the like, X<1> is a halogen, and 0<=n<4), e.g., TiCl4, in the presence of an electron-donating compound (e.g., benzoic acid). Then, an alpha-olefin (e.g., propylene) is polymerized by using a catalyst prepared by combining the above produced solid product with an organometallic compound (e.g., triethylaluminum).

Description

[Detailed description of the invention]

The present invention relates to a method for preparing Cχ-olefins, and more specifically, a specific activated titanium catalyst component and an organometallic compound J to 1,

This invention relates to a method for polymerizing α-olefins using a catalyst pv to produce highly stereoregular polyα-olefins with high activity. Conventionally, methods for stereoregularly combining α-olefins with a catalyst consisting of a solid catalyst component containing magnesium and titanium and an organometallic compound have been known; for example, Japanese Patent Publication No. 46-34098, IF!, p. Kosho 47-, i
2] 37. /If Kai-Sho fi2-9RO7G, JP-A Show 52
-1476f18. JP-A-53-109587.4'De Publication No. 56-5403. '
l'￥Kaisei 57-633
Examples include the method disclosed in No. 9. 12 or L, as described in Section 2, the f-similar medium used in the Pue method is manufactured through an extremely complicated process, so the properties of the medium are not constant, and as a result, the physical properties of the resulting 314 coalescence are The portrait quality is not sufficient. In particular, the degree of stereoregularity and reproducibility in polypropylene, polybutene, etc. is insufficient,
Improvement is desired. . The purpose of the present invention is to produce a stable K1jAl catalyst for 1 polymerization in a short time and in a simple process, and to produce a 3 polymerization catalyst with excellent stereoregularity.
The object of the present invention is to provide a method for producing a 14-coupled product with good 111 reproducibility and high activity. That is, the present invention provides (A) a solid catalyst component containing a magnesylano compound and a titanium compound, and It) ff
4t'! C containing a metal compound as a component: 1 (α using a medium
- In a method for polymerizing olefins, the general formula Mg(0
几り9 [In the formula, IL' is an alkyl group having 1 to 20 carbon atoms,
Schiff 6a'ki/1' group, aryl group or aralkyl group. ] was treated with alcohol, and then 11 was converted to the general formula Ti (O 2) 11xI4-n [
In the formula, 几2 is an alkyl group having 1 to 10 carbon atoms, cycloalkyl, Ji4. It represents an aryl group or an acylgyl group, and X+ represents a halogen atom. Further, 11 is a real number that does not satisfy 0≦T]<4. ], and the resulting solid product is used as the component (A) of the above catalyst. 2 Dos α-
JLIL union of olefins. Magnesilano dialkoxy 1° used in the present invention is. General 2 to 1g ((kawa,')9),
Here, ILL12 represents an alkyl group, cycloargyl group, aryl group, or acylgyl group having J-20 carbon atoms, preferably 1 to 10 carbon atoms, as described above. Preferred examples of magnesium dialkoxide include magnesium dimethoyacide, magnesium jetoxide,
Examples include magnesium diprobogide, magnesium dibutogide, magnesilano, dicyclohexoxide, and magnesium diphenoxide. Further, commercially available magnesium dialkoxides can be used, but those prepared by reaction of gold, silium, and alcohol may also be used. In Kinoi IJjJ, the magnesilano dialkoxide described in 2 is treated with AI call, but this alcohol-A
I no Jl.・IL: methanol, ethanol, glopanol, isopropanol, butanol, isobutanol, amyl alcohol, mekkunol, 2-ebruhexanol, allyl alcohol, crotyl alcohol, globargyl alcohol, cyclopentanol, cyclo Hegizanol. Examples include benzyl alcohol. The amount of alcohol used in this alcohol treatment is not limited to 1 and may be selected as appropriate depending on various conditions, but usually 0.01 alcohol is used per 1 mole of the magnesium dialkoxide. It should be ~2 mol, preferably between 0.002 and 1 mol. In addition, the temperature and time of this alcohol treatment may be determined as appropriate, but generally it is in the range of 0 to 150°C for 01 to 5 hours, preferably 20 to 100"C for 0.5 to 2 hours. Incidentally, in the above-mentioned alcohol treatment, a solvent such as pentane, hegizane, heptane, etc. can also be used.Furthermore, at Kihatsu 1JIJ, after performing the alcohol treatment, washing is performed if necessary, and the obtained product is It is necessary to react with a halogen-containing titanium compound in the presence of an electron-donating compound.The electron-donating compound present in the reaction system is generally an organic compound containing oxygen, nitrogen, phosphorus, or sulfur. .Specifically, amines, amides, chthones, dilyls, phosphines, phosphoramides, esters, thymeco-0-thyls, thyme esters, acid anhydrides, acids, esters, etc. Examples include organic acids, aldehydes, organic acids, etc. More specifically, organic acids such as benzoic acid, 11-oxybenzoic acid, and aromatic carboxylic acids: succinic anhydride, benzoic anhydride, Acid anhydrides such as p-toluic A-acid anhydride; archtone, methyl egul ketone; methyl f-butyl ketone, acetofuconone, benzophenone, benzoquinone li, any ketones having 3 to 5 carbon atoms: acetaldehyde, globimena A/dehyde,
octyl alahide, benzaldehyde. 2-1 carbon atoms such as tolualdehyde and nathaldehyde
5. Aldehydes; Gi-resistant? Mebyl, methyl nitrate, acid resistant edyl, vinyl lII'l acid, norovir acetate. Octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate9, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl meccrylate, ebul crotonate, ethyl hivalate, dimethyl maleate, ethyl cyclohexylcarboxylate, anhaka Notyl acid, ethyl benzoate, propyl benzoate, ammonium, ethyl acetate, octyl benzoate. An, cyclohexyl hexazoate, phenyl benzoate, ann ψl
Benzyl fomarate, methyl toluate, ethyl toluate,
Toluyl-Q-amyl, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
p-Butoxyammonium, ethyl B-sulfate. θ-Chloramin, 1′J ethyl chloride, ethyl naphthoate. r-butyrolactone, δ-valerolactone, coumarin,
Esters with 2 to 18 carbon atoms such as phthalide and ethylene carbonate; 2 to 1 carbon atoms such as acetyl chloride, benzyl chloride, toluic acid chloride, anisyl chloride, etc.
No. 5 acids/ra-r+-'; methyl ether, ethyl ether, isopropyl ether, n-'/thyl ether, amyl ether, tetrahydrofuran, anisole, Schiff: r-nyl ether, ethylene glycol butyl nylon and c ') Charcoal-, number 2 to 20 w-
Acid γ-amides such as acetate amide, benzoate amide, and torryl enzyme amide; tributylamine, N,N'-dimethylpiperazine. tribenzylamine, aniline, pyridine, picoline,
Amines such as tetramethylethylenediamine; acetonitrile, benzonitrile, torni) IJ /l'
Examples include l, c, dil, lyle; bootra methyl urethane, nidobenzene, lithium butylene): /j, etc. Preferred among these are Nisdel's, Nisdel's qI, ketones, and rr'8 anhydrides. In particular, alkyl esters of aromatic carboxylic acids, such as alkyl esters of aromatic carboxylic acids such as ammonium, (1, aromatic acid, p-, methoxyammon, 1L aromatic acid. Alkyl esters of numbers 1 to 4 are preferred, and benzoquinone, J, aromatic aromas such as b (chthone, ammonhydride, t1 aromatic acid), carboxylic acid anhydrides, 1L edel such as ethylene glycol butyl ether, etc. are also preferred. In addition, halogen-containing titane compound item-1 general formula Tj (OI
L2),, X'4-,, Halogen-containing 4 represented by Te
It is a titanium compound. Here, 几2I, carbon number 1 =
10 alkyl group, cycloalkyl group, aryl group or aralkyl group, a real number of 11 digits 0 or more and less than 4; , '1'10g4 * 'l'
j sword r41', 1. 'l i 41, [which titanium tetrahalide, T, t(0(Jll,)01.
, 'J'1(OCI, Tl5)0/, + Ti,
(On-(3411g)()l11.Ti(00g
, tl, 1) Trihalogenated alkoxydicnes such as Ur, 1, Tj(0011,l)g□JI T! I'1(
0(3911,)901. l i'j (011-0
411,), O7,,'l'1(00,Jl,),C!
/! Dihalogenated alkoxybutane such as Q, T i
(0OJ(s)nC1,'l'1((1(]JII,
)IIOl, ', IJ (011-04119
), 0/! ,'[! Examples include monohalogenated trialkoxytitanium such as No. 1 (OCQITR) and Jlr. These may be used as a mixture in both China and Germany. Among these, it is preferable to use a material with a high halogen content, and it is sometimes preferable to use titanium tetrachloride (1'lo/4). Various methods can be considered for reacting the 41; acid obtained by the above-mentioned alcohol treatment with a halogen-containing titanium compound in the presence of an electron-free (power compound). For example, (1) the above-mentioned formation (2) A method in which a substance is first reacted with an electron synergistic compound and then a halogen-containing titanium compound is added to this system to react, or (2) an electron-donating intervention and a halogen-containing titanium compound are added to the above product. Same 1
In addition to 1'j, a method of stirring the reaction may be considered. There are no particular restrictions on these conditions for conceiving, and they can be selected as appropriate depending on various conditions. To the product obtained by the treatment, a compound of 0.001 to 1/1.001 to 1/1.
5 moles, 01 years old Shimoyo 11. (15~1:(, le f
11j ba[Additionally: lTh, '? K&'j, 0
~2 (1 (1" CK Te54) ~511-1, peg or 20 ~] React at -C for 20 minutes to 3 hours. Next, add a halogen n-containing titanium compound to the reaction system. 0.03 to 1 mole of magnesilano in the product
Add 100 mol, preferably in the range of 0.1 to 20 mol, and add 10 to 20 (from 3 () minutes at 1" C) for 0 hours, preferably L < kit, 1 to 511 i' at 30 to 150°C.
Stir the reaction for 1 minute. In this reaction, if necessary, it is also possible to use an inert solution ρIL such as j+ --, butane, etc. After the reaction is completed, the solid product obtained in step 1 is thoroughly washed with an inert solvent such as n-hebutane. After the reaction, it is preferable to remove only the liquid and repeat the above-mentioned addition of the halogen a-containing titanium compound and the reaction, since the solid product can be catalyzed and the t1 capacity of C can be improved by -1. In the present invention, the component (A) of the thus obtained solid/IE product acid α-olefin lt synthesis catalyst (solid oil fl
component). According to the present invention, the above solid product is the component (4),
In addition, an organometallic compound was used as the 0() component. (A), ω)
Polymerization of α-olefins is carried out using a catalyst consisting of two components: /II/; In the polymerization of α-olefins, liquid J and O
The organometallic compound as a component is added, and then α-
Introducing olefins. 1. The combination method and conditions are not limited to /l'&, and include solution polymerization, suspended H+M Jri combination, and gas phase Jlj combination.
Any of z is possible, and also continuous polymerization, non-continuous polymerization #9

[,
Both of these acquaintances are possible and occur. Addition 171 of the catalyst component is
Taking the case of solution J■ polymerization or suspension polymerization as an example, (4
) component converted to titanium atoms, Q, (101~5.0
mmol/II, preferably l', t(1,00Fi=
1.0 m') mole, 71 tol, (13) composition f
j to the titanium atom in component (A) °C1 to 1000
(molar ratio), preferably 5 to 500 (molar ratio). Incidentally, in addition to the above ii; (A) and (11) components, an electron-reactive substance as described above can also be added. In addition, the α-olefin pressure in the reaction system is always between 7E and 50.
is preferred, and the reaction temperature is 20-300'C, preferably 50-250'C. At the 11th conjunction, the molecule 1 of ゛[
11 adjustment can be done by known means, for example hydrogen In, f from row 1
,【I can. The reaction time may be appropriately selected from 0.1 to 10 hours, preferably from 0.5 to 5 hours. The catalyst used in the method of the present invention has 11i metal compounds as components, and the IF"iK limit is r. The gold 14 contained in this organometallic compound is t, lithium, sodium, potassium, zinc. cadmium 2. aluminum 1. (Although there are several, aluminum is particularly preferred. Compounds containing aluminum, 1. c. Organic alumina J.) There are no limitations, and those represented by the general formula At 4 m x 2.l □ are widely used. 4 is an argyl group with a carbon number of 1 to 1 o, Schiff 1 is a core alkyl group, and 1 spanning aryl group, and In is 1 -30, and X2 does not represent a halogen atom such as chlorine or bromine.Specifically, trialkylaluminium compounds such as trimethylaluminum, triethylaluminum, triimpropylaluminum, triisobutylaluminum, triethylaluminum, etc., and diethylaluminum Dialkylaluminum monohalides such as monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum monochloride are preferred, and mixtures thereof are also preferred. -Olefins are usually those represented by the general formula R3-0rl=OIT (Book 1, 8 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group), such as ethylene, propylene, butene- 1, hexene-1, ocd. Including direct @4 monoolefins such as No.1, branched monoolefins such as 4-methyl-pentene-1.Dienes such as butadiene The present invention can be effectively used for the combination of these 111.G, or the combination of various α-melefins.According to the method of the present invention, the catalyst to be used can be prepared in a short time and with Because it is carried out in the process, oil sand with uniform properties of 1 and C is always obtained, and as a result, the physical properties of the polymer to be produced are very well reproduced.
The activity of the catalyst used in the IJ method is extremely high, the stereoregularity of the resulting polymer is high, and the bulk density is also large (and the 5'M product value is particularly high). Therefore, since the method of the present invention yields a polymer with high activity, JJI synthesis, C, steric II, and other properties, it is possible to obtain polymers with high activity, i. Is it possible to abbreviate the extraction process?
iJ ability and very efficient polymerization 1. Next, we will show examples of the present invention. All operations in the following examples were carried out once under an argon stream. Oh (・fl・+! 41)
The activity t and stereoregularity coefficients (r, ], ) were defined as follows. Oil sand, live 1 I 1 Ni 0”c, 2 hours, propylene partial pressure 7
11 tons (kg) of the total polymer produced per titanium atom in the polymerization under conditions of 1 kg/cm''. Example 1 (1) Solid h.
15 Q ml of dehydrated and purified T1-heptane was placed in four 1" flasks each having a volume of 100 me (8 mmol) of magnesium diconitoxide.
, j7. Person 1-1 (I'/, stirring 1.), isopropyl alcohol 1.0 (i 9 (, 17.5 mmol)) was added to C, and the temperature was raised to 80°C and treated for 1 hour. was cooled to room temperature, supernatant 71k was taken out, 150ml of n-hebutane was added, stirring and extraction were repeated twice for washing, and then 150ml of n-hebutane + 2.63ml of ethyl benzoate (175 mmol) and four JX1 (
How much titanium chloride 83 (440 mmol)? Jl1
Rising to the point? JIAl/, 2 hour reaction saceta. After reaction)
! Lower the power to 0°CK, let it stand, and let it stand. Remove the α liquid and add 150 m/! of 11-heptane! Add, stir,
Washing was performed by repeating standing still and draining the liquid twice. after that,
Add 83% of butane tetrachloride again, react for 1 hour until the boiling point, let it stand, then drain the liquid, then add n-butane, stir, let it stand, and drain the liquid. ions are detected and the b14 purification is repeated until the solid/T
lt media component (A) ''; a: 1!'). When T1 in the obtained solid catalyst component was determined by colorimetric method, it was 411 of mo, ttiH&-1,48m9-1'
j/So River body. (2) Polymerization of propylene 1: φ, in a dry 11 volume stainless steel autoclave, degassed and purified n-heptane 4 (1 (l me,
2.0 mmol of triethylaluminum, p) methyl chloride ('J,'M) 0. G mmol Jd and soil F! +, fl+ to T
i, CO, (12 mm+) mole and 70”CKJf1
It was warm. Then hydrogen 1), 2 k! ? /cm”a4
In addition, propylene was continuously fed at a propylene partial pressure of 7 kg/cm2, and polymerization was carried out at 70'C for 2 hours. 184 ml of white polypropylene powder was obtained.The 1.I of the obtained polypropylene was 198.0%, and the bulk density was 0.:13 l/rnl.In addition, the liquid phase was evaporated. , IJ- soluble 1(1
, 6.8 ml of polymer were recovered. Examples 2 to 10 (1) Production of solid catalyst component In Example 1 (1), the following method I was carried out using a prescribed alcohol instead of isoplj-vinyl alcohol. The solid catalyst component (A) is M
'M-made Shibuko. Method 1: Same method as in Example J(1). Method: Washing of the initial magnesium compound after alcohol treatment 1 [Example 1 (1) except that the culm was omitted]
). Method 111: Magnesilano, compound, solvent, and alcohol were added to the flask, and treated at 40°C for 1 hour. Next, an electrodynamic compound and a titanium compound were also added to the system, and the system was treated at 105"C for 72 hours. After that, lower the temperature to )?
After draining the liquid and washing, add titanide and incubate in the same manner as in (1).
(2) Polymerization of propylene In a dried 1/volume stainless steel autoclave, 400 ml of degassed n-hebutane (1'J1:A), (1'J1:A), diethylaluminum No・ritl IJ do(:+)l<At+ ) +,; and■)-Toluyl rI'2 Mekuru's place 5i'! , and the solid catalyst obtained in (1) above, the components are L・l
Add 0.02 mmol of pyrene and raise the temperature to 0°C.Next, add hydrogen Q, 2 kg/cm', and make pyrene J, TE 7 kg/'c+n'. Probile / was supplied as I + 1! at 70°C.
Time Jlj met. After the reaction is complete. White polypropylene powder was obtained by removing unreacted gas and further passing through f-1. The properties of the obtained polypropylene are shown in Table 1. Example 11 (1) Production of solid catalyst component ('jIJ 1 (Example 1 (1) except that 1.069% of isozorobyl alcohol was added in 11)
The same operation as above was performed to obtain a solid catalyst component (4). (2) Polymerization of ethylene Degassed and purified 11-hepta:y 400 me, 'l'F was placed in a 1e capacity stainless steel autoclave.
A 2 mmol l J) EACj 2 mi! J mole o”
, and the above +11 gives 1 (I solid touch IJ formation 5) Moxibustion'
0.02 mmol of l' i was added and the temperature was raised to 80°C. Next, 3 kg/cu2 of hydrogen was added, and the total pressure was maintained at 12.5 kg/c+a' with ethylene.
The mixture was heated to 0°C for 1 hour. After the reaction was completed, unreacted gas was removed and the mixture was further passed for 1 hour to obtain a white polyethylene powder.
Comparative Example 1 (1) Preparation of solid catalyst component Into a well-dried four-loaf flask with a volume of 50 (l me), 150 me of dehydrated and purified 11-heptane, maf.
, i, 10.0 g (88 mmol) of sium diethoxide and 2.049 g (J 7.6) of ethyl benzoate
Add MiIJmol) to 1 lil! The reaction was carried out for 1 hour under flowing conditions. Next, the temperature was raised to 70°C and titanium tetrachloride 839 (
4/IO mmol) was added dropwise between 30 and 30 mm, and the mixture was reacted under reflux for 3 hours. Then, the temperature was lowered to 0°C and the supernatant liquid was removed. Add 250 ml of n-hebutane, stir for 1η, let stand, and drain the liquid.
It was returned and washed to obtain a solid catalyst component. (2) In Example 1 (2) for the 1n synthesis of propylene, the solid catalyst component was
Example 112) except that the one obtained in ) was used.
I performed the same operation as above. The results are shown in Table 1. Comparative Example 2 (1) Production of solid catalyst component Example 1 (Example 10 except that phenol was used instead of isopropyl alcohol in 11)
A solid catalytic pIL component was obtained by performing the same operation as above. (2) In Propylene Polymerization Example 11211C, -1-
The same operation as in Example (2) was carried out except that the product obtained in nj'4 (1) was used. The results are shown in Table 1.

Claims (1)

[Claims] (+) (A) A solid catalyst fJ'/: component containing a magnesium compound and a titanium compound; The key to the polymerization method is (1g (011,') to the general formula,
[In the formula, IL' is alkyl 7i+ having 1 to 20 carbon atoms;
, cyclor1 alkyl group, aryl group or "L afurkyl JI" is treated with alcohol, and then in the presence of an electron-dynamically modified compound (a), a magnesilano dialkoxide of the general formula Tt ( csu(,”)+1”
4-n In the formula, ■ and 2 are ``alkylno, (, cycloalkylno, (, aryl group) or (-1
-Aralgyl jJ- is L, X'k: I- is a halogen atom. :Y is a real number that satisfies (lSn < 4.) J+ is a solid product obtained by reacting with a halogen-containing titanium compound -tYl of the above catalyst (A). A method for the monopolymerization of α-olefins, which is characterized in that it is used as a component. (2) Magnesilano, dialkoxide represented by the general formula
. Magnesilano dibutogicide, Magnesium dibrobogicide, Magnesilano dibutogicide, ′? Patent W which is gnesium dicyclohexogiside or magnesium diphenogiside [described in claim fliα, item 1, item 1, 311. (31TI7. The method described in Patent No. 111, #rl, in which the compound is an organic compound having an acid (, nitrogen, phosphorous) or t+if+: Yl7, item 3. (4) The gold compound is an organic compound containing lead, cadmium, or aluminum. Claims [11-1]. The method described in Section 1. f! 31 t*-ov :y-(y is general formula I
L3-(jJl=(,!I+, (wherein, 3 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group -1) - 'L5' n
'I' R: 'The method according to Claim Qiix, Paragraph 1, Mt.