JPS585311A - Catalytic component for olefin polymerization - Google Patents

Abstract

PURPOSE:A catalytic component having a high activity and providing polymers with good properties, prepared by contacting a silicon halide with a solid composition consisting of a magnesium dihalide, a titanium tetraalkoxide and a polymeric silicon compound. CONSTITUTION:A catalytic component for olefin polymerization, which is a product prepared by contacting a silicon halide (e.g., SiCl4) with a solid composition consisting of a magnesium dihalide (e.g., MgCl2), a titanium tetraalkoxide [e.g., Ti(OC2H5)4] and a polymeric silicon compound of the formula, wherein R is a hydrocarbon residue, e.g., methylhydrogenpolysiloxane. It is possible to produce a polymer with good properties in high activity by polymerizing an alpha-olefin with the aid of a Ziegler catalyst having the solid catalytic component as a transition metal component.

Description

DETAILED DESCRIPTION OF THE INVENTION α] BACKGROUND OF THE INVENTION Technical Field The present invention provides a catalyst component vc@ that provides a polymer with high activity and good m4 mer properties.

Conventionally, magnesium compounds such as madanesium halide and magnesium oxyhalide.

Dialkylmagnesium, alkylmagnesium halide, magnesium alkoxide, ``*t, - to 1゜dialkylmagnesium Q-complex with organic aluminum, etc. can be used as carriers for transition metal compounds such as titanium compounds. It is known that catalysts can be obtained, and many proposals have been made.

In these prior art techniques, although the catalytic activity is high to some extent, the 4-reamer properties of the produced polymer are not sufficient, which is a foreshadowing that requires improvement. Polymer properties are extremely important in slurry polymerization, gas phase polymerization, and the like. for example,
If the polymer properties are poor, problems such as polymer adhesion within the polymerization tank and difficulty in extracting the polio from the polymerization tank are likely to occur.Also, the polymer concentration within the polymerization tank is closely related to the II properties. - Unless the remer properties are good, the temperature in the polymerization tank cannot be increased.The fact that the polymer concentration cannot be increased is extremely disadvantageous in terms of industrial production.

According to the prior art Japanese Patent Publication No. 1851-37195, a method has been proposed in which magnesium halide or the like is reacted with titanium tetraalkoxide and further reacted with organoaluminium.

According to JP-A-54-16393, a method is proposed in which magnesium halide or the like is reacted with titanium tetraalkoxide cape, and then a halogen-containing compound and a reducing compound are reacted.

(6) Summary of the Invention The purpose of the present invention is to provide a solution to the above-mentioned problems, and to achieve this purpose by means of a supported transition metal catalyst component prepared in a specific manner.

[Accordingly, the catalyst component for olefin polymerization according to the present invention is characterized by being a contact product of (N to (B)) below.

Components (N!) A solid composition composed of a polymeric silicon compound containing magnesium dihalide and titanium tetraalcohol.

Component (B) Of silicon!・Rogen compounds.

Another catalyst component for olefin polymerization according to the present invention is the following component (also characterized by being a contact product of Al-(C)).

Component (A): A solid composition composed of magnesium silica/tinide, I-rimer silicon compound containing titanium tetraalcohol. Component (B): A silicon compound.

Component (q is a polymeric hydrocarbon residue having a structure represented by formula -81-0-) Effect Polymerization of α-olefin using the solid catalyst component according to the present invention as a transition metal component of a Ziegler catalyst and,
A polymer with high activity and excellent I-remer properties can be obtained. The reason why a polymer with high activity and good polymer properties can be obtained is not necessarily clear, but it is due to the chemical interaction of the components used in the present invention and the special physical properties of the solid component (A) used and the catalyst component produced. This seems to be due to

[Brief explanation of drawings]

1.g Minutes (4) l) Composition Component (4) is a solid composition composed of dinoS magnesium rhodanide, titanium tetraalkoxide and certain polymeric silicon compounds. This solid composition (Al is not a magnesium dihalide or a complex of magnesium dihalide and titanium tetraalkoxide (it is a different solid).At present, its contents have not been fully analyzed, but one composition analysis According to the results, the solid IIfl composition contains titanium, magnesium, halogen, and silicon, and the molar ratio of halogen to magnesium is 0.4 or more and less than 2, preferably 1.0 to 1.
．． 8 and seems to be a different compound from the magnesium dihalide used as a raw material. The specific surface area of this component (1) is often small [usually 10
m"7g or less, and most of them are 3m"7g or less. In addition, according to the results of X-ray diffraction, no peak associated with magnesium dihalide was observed at all, and even from an X-ray perspective, it seems to be a different compound from magnesium dihalide. , produced by mutual contact of magnesium dihalides, titanium tetraalkoxides and certain polymeric silicon compounds. (1) Magnesium dihalides such as MgF2. MgC1, MgBr,
etc. (2) Titanium tetraalkoxide, for example, Ti(QC2H6)4. TI(0-fl
oe, H,). Ti(0-nC4H,)4. TI(0-nC3H,)
, , Ti (0-i@0c4H,)4゜Ti (0-
CH2CH(CH3)2)4. Ti(0-C(CH3
)3) 4゜Ti(0-CIsH1□), ,Ti(0-
C, fll, ), , Ti (0-fic, I'11.
)4゜Ti[0CR(C,H,)2],, TI(OC
R(CH8)C,H,), . Ti(QC,H□,)4. Ti(QC□.H8,)
i[OCH,0H(C2H,)C4H,], etc. (3) Polymer silicon compound In the formula -81-0-, R is a hydrocarbon residue having about 1 to 10 carbon atoms and about 1 to 6 carbon atoms per 1%. Specific examples of polymeric silicon compounds having such structural units include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane,
Examples include cyclohexylhuman a/resiloxane. The degree of polymerization is not particularly limited, but considering handling, the viscosity is between 10 centistokes and 10 centistokes.
It is preferable that the thickness be about 0 centistokes. Although the terminal structure of the hyP-lolysiloxane does not have a large effect, it is desirable that it be capped with an inert group such as a trialkylsilyl group. (4) Contact of each component (amount ratio) The amount of each component used is as long as the effect of the present invention is recognized.
It can be anything, but in general. It is preferably within the following range. The amount of titanium tetraalkoxide to be used is preferably within the range of 0.1 to 100% (preferably within the range of 1 to 4%). The amount of the compound to be used is within the range of 1 x 10 to 100 (in a molar ratio of 1 to magnesium dihalide, preferably within the range of 0.1 to 1 O. (Contact method) of the present invention) Component (A) is obtained by contacting the three components described above. The contact of 3 g can be carried out by any generally known method. -100°C to 200°C, preferably θ The contact time is usually 10 minutes to 10 minutes, preferably 0.5 to 5 hours.The three components are brought into contact with each other under stirring. It is preferable that the particles are brought into contact with each other by mechanical powder 19IK using vibrations and vibrations.The order of contacting 3IlL may be arbitrary as long as the effect of the present invention is observed. Although possible, it is common to first contact the magnesium dihalide and the titanium tetraalkoxide and then contact the polymeric silicon compound. Contacting the three components can also be carried out once in the presence of a dispersion medium. In that case, Examples of dispersion media include hydrocarbons, halogenated hydrocarbons, dialkyl polysiloxanes, etc. Specific examples of hydrocarbons include hexane, hebutane, toluene, and cyclohexane; Examples include n-butyl mide, 1.2-J)l chloroethylene, carbon tetrachloride, chlorobenzene, etc., and specific examples of dialkylbolysiloxane include dimethylpolysiloxane, methyl-phenylpolysiloxane, etc. 2. Component (B) Component (Bl is a halogen compound of silicon. A compound represented by the general formula R, 8iX. (Here, R1 is a water bulk or hydrocarbon residue, , X is a halogen, and n is a number of 1 < 4).Specific example Toshiko+'X -5tc14- Hatcla
, cH8Sicl, . 8iBr, , (C2H,)281C12, (CI(
, )3SiC1, etc. 3. Component (C) Component (q is used according to necessity and is a polymer silicon compound. This polymer silicon compound is the same general polymer as the polymer silicon compound to be used for the production of component (N). Synthesis of the catalyst component of the present invention The catalyst component of the present invention is defined by the formula. Component (Al-(B■ or component (
It is a contact product of At-(Q. l) Amount ratio The amount of each component used is as long as the effect of the present invention is recognized.
Although it is arbitrary, it is generally preferred that it be within the first order range. The amount of component (Bl used is 1xlO to 1 in molar ratio to the magnesium halide that constitutes the solid component (A))
It may be within the range of 00, preferably. It is within the range of 0.1 to 10. The amount of component (C) to be used is 1 x 10 molar ratio to the magnesium sulfur atomide that constitutes the solid component (A).
-10, preferably 0.05-3.0
is within the range of 2) Contact method The catalyst components of the present invention are the solid components (A) and K component (B) mentioned above.
) and optionally component (C) 4. It is something that The contacting method can be carried out by any generally known method. Contact is general k. -100°C to 200°C, preferably 0°C to 70°C, may be contacted for 4 hours. The contact time is usually between 10 minutes and 1 hour, preferably between 0.5 hours and 5 hours. It is. Solid components (Al and component (B) and optionally component (C)
) is preferably brought into contact with stirring, and --
Contact may be carried out by mechanical grinding using a mill, vibration mill, etc. The order of the contact may be arbitrary as long as the effects of the present invention are observed. Solid component (A
Component (B) may be reacted with I first (or component (C) may be reacted with I first.) Components (AJ and components (B) to (q) may be brought into contact with each other at the same time in the presence of a dispersion medium. In that case, the dispersion medium used in the production of component (A) may be 5. Polymerization of α-olefins l) Formation of catalyst The catalyst component of the present invention can be used in combination with an organometallic compound as a cocatalyst to polymerize α-olefins. It can be used for polymerization. Any organometallic compound of a metal of Groups 1 to 2 of the periodic table, which is known as a cocatalyst, can be used. Particularly preferred is an organoaluminum compound. As a specific example, the general formula Ri
-nAIX, or ILnee mAl (OR')
nn (where R, R, and R are hydrocarbon residues or water volumes of vertical prime numbers 1 to 2o&i degrees, which may be the same or different, X is a halogen atom, and n and m are each 0<n<2.0 There is a number expressed as 1. Specifically, (a) trimethylaluminum, trie f
aluminum, triisobutylaluminium. tridecylaluminum, tridecylaluminum, etc., trialkylaluminium monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, C alkylaluminum halide, (/→ diethyl aluminum hydride,
Examples include dialkylhyP rides such as diisoditylaluminum hydride, and alkylaluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum butoxide, and diethylaluminum ethoxide. Addition of other organometallic compounds 1, such as RLaAl(Ot-White 3
．． R and R8 have 1 carbon number and may be the same or different
It is also possible to use an alkylalunium alkoxide represented by the following formula (which is a hydrocarbon residue of about -20). Examples include the combination of triethylaluminum and diethylaluminium ethoxide, the combination of diethylaluminum monochloride and diethylaluminium ethoxide,
Examples include the combination of ethylaluminum dichloride and ethylaluminum ethoxide, and the combination of triethylaluminum chloride, diethylaluminum chloride, and diethylaluminum ethoxide4. Although there are no particular restrictions on the amount of these organometallic compounds used, , is preferably within the range of 0.5 to 1000 in a weight ratio of 1 to the solid catalyst component of the present invention. 2) α-Olefin The α-olefin polymerized with the catalyst system of the present invention has the general formula R
-CH=CH2 (where R is a hydrogen atom or has 1 carbon number
~10 hydrocarbon residues, which may have substituents. ). Specifically, ethylene, propylene, butene-1, pentene-1, hexene-1,
There are olefins such as 4-methylpentene-1. Especially preferably. Ethylene and propylene. In these polymerizations, 'C50 weight percent relative to ethylene. Copolymerization with the above α-olefins can be carried out, preferably in a weight percentage of 1. Further, co-X+ can also be carried out with copolymerizable monomers other than the above α-olefins (for example, vinyl acetate and diolefins). 3) Polymerization The catalyst system of the present invention can be applied not only to ordinary slurry polymerization, but also to continuous polymerization in liquid-phase solvent-free polymerization, solution polymerization, or gas-phase 1 method, which uses substantially no solvent. It can also be applied to batch polymerization, or 5 methods in which preliminary polymerization is performed. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures. The polymerization temperature is from room temperature to about 200°C, preferably from 100°C to 15G°C, and hydrogen can be used as an auxiliary molecular weight regulator at this time. Also, by adding a small amount of TI(OR)4-nX during polymerization (where R is a hydrocarbon residue having about 1 to 10 carbon atoms, X is a halogen, and n is a number in the range 0 < n < 4), It is possible to control the density of the polymer that is polymerized. Specifically, it can be controlled within a range of about 0.890 to 0.965. 6. Experimental Examples Example-1 1) Solid component (dehydrated and deoxygenated N
-50 heptane? Introduced lytol and then MgC1
, and 0.2 moles of Ti(0-nBu)4 were introduced, and the reaction was carried out at 90"C for 2 hours. After the reaction was completed, the temperature was lowered to 40°C, and then methylhydrodiene polyamide was added. 12 milliliters of siloxane (20 centistokes) was introduced and reacted for 2 hours.The produced solid component was washed with n-heptane and a portion was taken out for composition analysis. ,
C15 = 11.7 weight percent, Mg = 5.3
, G-cent, 8i-1.5 weight percent. Also, when the specific surface area was measured using BETtI:, the specific surface area was too small to be measured, but it was estimated that 1 m
2) Production of catalyst components Dehydrated and deoxygenated N
- 50 ξ liters of hebutane was introduced, and the entire amount of the solid component (A) synthesized in the upper stage was introduced. 0.06 mol and 50Z liters of n-hebutane were introduced and reacted at 50°C for 2 hours. After the reaction was completed, it was washed with n-heptane to obtain a catalyst component. When a portion was taken out and analyzed for composition, TI = 3.2 weight no cents, M
3) Polymerization of ethylene. A stainless steel autoclave with an internal volume of 1.5 liters, equipped with stirring and temperature control equipment, was subjected to vacuum-ethylene displacement. After repeating this several times, 800 milliliters of n-hebutane, which had been sufficiently dehydrated and deoxygenated, was introduced, and then 10 grams of triethylaluminum 200i IJ grams and the catalyst component synthesized above were introduced. The temperature was raised to 5°C, Hydrogen was introduced at a partial pressure of 4.5 Kg7cm, and ethylene was further introduced. Polymerization was carried out for 3 hours at a total pressure of 9 ~/cm''. During the polymerization, these reaction conditions were kept the same. However, the pressure decreased as the polymerization progressed, so that only ethylene could be removed. After the polymerization, which was maintained at a constant pressure from K, the ethylene and hydrogen were purged, the contents were taken out from the autoclave, and this 4 remer slurry was filtered.
I dried it in the dryer overnight. 116/Lam polymer (P
IC) was obtained [catalyst yield (g-PH7g-solid catalyst component) = 11.6001° for this polymer 19
Melt 7 explosion rate (M
F'R) was measured and found to be MFR=13.7. 4 Lima bulk specific gravity = 0.48 (g/cc). Example-2 In the production of solid component (4) of Example-1, T1 (0
-nBu), except that the amount used was 0.15 mol, the solid component (A) was produced in the same way, the catalyst component was produced in the same way, and the polymerization of ethylene was also produced in the same way as all (nBu). A polymer of 125 duram was obtained [yield based on catalyst (g-PE7g/solid catalyst component): 12.500]
. MP'Rw9.7, polymer bulk density 0.38
(g/cc). Examples 3 to 4 All catalyst components were produced in the same manner as in Example 1, except that the amount of 8iCI4 introduced and the reaction temperature were changed to 5 as shown in Table-IJC. The results are shown in Table 1K. Example 5 In the production of the catalyst component of Example 1, 8iC14 was replaced with K, SsC140.04 mol and methyl-
The active catalyst components were produced in exactly the same manner, except that 12 liters of Hyde Kasumi Diene Polysaccharide AΦsan 12 (liters) were introduced and reacted at 70°C for 2 hours.As a result of compositional analysis, T
i=15.5 weight percent), Mg-6.93 weight percent), CI==g35.8 weight percent. Polymerization of ethylene was also carried out in exactly the same manner as in Example-1. A polymer of droplet duram was obtained [yield based on catalyst (g-PE
7g/solid catalyst component) = 10,6000]. MFR=11.5, polymer bulk specific gravity! 0.45
(g/cc). Examples 6 to 8 Using the catalyst components of Example 3, ethylene polymerization was carried out in exactly the same manner except that the organic alkali (xlam) component was changed as shown in Table 2.The results are shown in Table 2. Example 9 This example concerns the polymerization of an ethylene-butene-1 mixed gas. Using the solid component prepared in Example-1, butane-1 was added in place of ethylene in 7. Polymerization was carried out under exactly the same conditions except that an ethylene-butene-1 mixed gas containing 5 mol cents was used and the H3 concentration in the polymerization tank was increased to 1 molar cents. 256 grams of polymer was obtained. .VFR-2,1,/Remar bulk density w = 0.43 (g/cc), if: Remar density -0
,933(ν'cc). Example-10 Jin's example! This relates to the polymerization of a-pyrene. 800 milliliters of sufficiently dehydrated and deoxygenated n-hebutane was introduced into the autoclave used in Example-1, and then [triethylaluminum 385 (IJ/
Rum, 123 grams of ethyl noratolylate,
And 28 haligrams of the catalyst component synthesized in Example-1 was introduced. 6℃, and 9! /am” for 2 hours. 29 g of I remer was obtained. T-1,
1,-76 weight of 9-cents, product-1, I, =93
Weight/#-cents. 105-

Claims (1)

[Scope of Claims] L A catalyst component for olefin polymerization, designated as 4111, which is a contact product of components (4) to (B) below. Component (4) Danesium dihendide, titanium detraalkoxide, and I-- having the structure represented by -8N-0-
A solid composition consisting of a silicon compound, where R is a hydrocarbon residue. Component - Silicon Halogen Compound 2 Olefin polymerization catalyst component/component (A), which is a contact product of the following components (4) to (C).
I Magnesium dihalide, titanium tetraalkoxy P
% and -5t-O--, where R is a hydrocarbon residue. Component (B) silicon halogen compound component (q having the structure represented by the formula -8i-0-/IJ Maq 1) - silicon compound (where R is the same or different from the above R) hydrogen residues).