JP3423370B2 - Olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] The present invention relates to a catalyst for olefin polymerization.
It is about. More specifically, the present invention provides
High standing when applied to the polymerization of olefins with a prime number of 3 or more
It has regularity and can control the molecular weight distribution of the polymer.
Olefin polymerization catalyst. Conventionally, a magnesium-supported high-activity catalyst has been used.
The olefin polymer obtained by using
In general, the molecular weight is lower than the polymer obtained using
It is known that the cloth is narrow. Therefore, when the polymer melts
Is poor in flowability, and problems remain in moldability. So, in the past
Is a method to broaden the molecular weight distribution by a specific polymerization method
Was often taken. For example, two or more polymerization tanks
Used to produce multiple polymers with different molecular weights,
To obtain a polymer with a broad molecular weight distribution.
There is a method. However, this method does not
In order to obtain a polymer with a molecular weight distribution
In many cases, the production capacity of the tank must be reduced.
This often led to higher costs. Like this
Those who use several polymerization tanks with reduced capacity
The desired olefin polymer is only one polymerization tank
Need to be more efficient
Nor. Therefore, without using multiple polymerization tanks,
Of magnesium-supported catalyst to give polymer with wide distribution
A proposal has been made. For example, JP-A-3-7703,
JP-A-2-170803, JP-A-4-136006
And JP-A-4-239008, it is disclosed that magnesium
Donating electrons during polymerization using a catalyst component
Polymers with a wide molecular weight distribution using two or more kinds of polymers
A way to do that has been proposed. But these things
As far as the inventor knows, the activity and the steric nature of the resulting polymer
There seems to be a problem in terms of regularity, etc.
I'm in a situation where I can't help. [0003] The present invention is to solve the problem.
Is to solve the above-mentioned problem. [0004] [Means for Solving the Problems] [Summary of the Invention] <Summary> The present inventors have proposed the use of a specific catalyst.
The present invention has been found to be able to solve the above-mentioned problems.
Reached. That is, the catalyst for olefin polymerization according to the present invention.
The medium comprises the following components (A) and (B):
It is a feature. Component (A): titanium, magnesium, halogen and below
A silicon compound represented by the following general formula as an essential component
Ziegler-type catalyst solid components R¹R² _3-nSi (OR³)_n (Where R¹Is a branched aliphatic hydrocarbon residue or alicyclic
The hydrocarbon residue is represented by R²Is R¹Same or different carbonization as
A hydrogen residue is represented by R³Represents a hydrocarbon residue, and n represents 1 ≦ n ≦ 3
Number, respectively) Component (B): a reaction product of the following components (i) to (ii):
Organometallic compound components. Component (i): General formula [0005] Embedded image A boron compound represented by the formula (where R⁴Is carbon number 1 to 1
0 hydrocarbon residues. ) Component (ii): organoaluminum compound <Effect> When the catalyst according to the present invention is used, high activity and three-dimensional
Magnesium bearing with a well-regulated and well-known molecular weight distribution
Obtain polymer wider than polymer obtained using supported catalyst
be able to. [Specific description of the invention] << Olefin polymerization catalyst >> Olefin polymerization according to the present invention
Catalyst comprises a specific component (A) and a specific component (B).
Things. Here, "consisting of" means that the component is
Only for indications (ie (A) and (B))
It does not mean that
Does not exclude coexistence of components. <Component (A)>Structural component The component (A) of the catalyst according to the present invention includes titanium, magnesium and the like.
, Halogen and siliconization represented by the following general formula
Ziegler-type catalyst solid containing the compound as an essential component
Component. R¹R² _3-nSi (OR³)_n (Where R¹Is a branched aliphatic hydrocarbon residue or alicyclic
The hydrocarbon residue is represented by R²Is R¹Same or different carbonization as
A hydrogen residue is represented by R³Represents a hydrocarbon residue, and n represents 1 ≦ n ≦ 3
Magnesium used in the present invention)
Magnesium compounds as magnesium source
Umdihalide, dialkoxymagnesium, alkoki
Simium magnesium halide, magnesium oxyhalai
, Dialkylmagnesium, magnesium oxide, hydroxyl
Magnesium oxide, magnesium carboxylate, etc.
Can be Of these, magnesium dihalide is preferred.
New Further, a titanium compound serving as a titanium source is one of
General formula Ti (OR⁵)_4-pX_p(Where R⁵Is hydrocarbon
A residue, preferably one having about 1 to 10 carbon atoms,
X represents a halogen, and p represents a number satisfying 0 ≦ p ≦ 4).
And the compounds mentioned. As a specific example, TiC
l₄, TiBr₄, Ti (OC₂H₅) Cl₃, Ti
(OC₂H₅) Cl₂, Ti (OC₂H₅)₃Cl, T
i (O-iC₃H₇) Cl₃, Ti (O-nC₄H₉)
Cl₃, Ti (O-nC₄H₉)₂Cl₂, Ti (OC
₂H₅) Br₃, Ti (OC₂H₅) (OC₄H₉)₂
Cl, Ti (O-nC₄H₉)₃Cl, Ti (OC₆
H₅) Cl₃, Ti (O-iC₄H₉)₂Cl₂, Ti
(OC₅H₁₁) Cl₃, Ti (OC₆H₁₃) Cl₃, T
i (OC₂H₅)₄, Ti (O-nC₃H₇)₄, Ti
(O-nC₄H₉)₄, Ti (O-iC₄H₉)₄, T
i (O-nC₆H₁₃)₄, Ti (O-nC₈H₁₇)₄,
Ti [OCH₂CH (C₂H₅) C₄H₉]₄Etc.
I can do it. Further, TiX '₄(Where X 'is a halogen
Molecular compound obtained by reacting an electron donor described later on
The material can be used as a titanium source. Such a minute
Specific examples of the child compound include TiCl₄・ CH₃COC
₂H₅, TiCl₄・ CH₃CO₂C₂H₅, TiCl
₄・ C₆H₅NO₂, TiCl₄・ CH₃COCl, T
iCl₄・ C₆H₅COCl, TiCl₄・ C₆H₅C
O₂C₂H₅, TiCl₄・ ClCOC₂H₅, TiC
l₄・ C₄H₄O and the like. Further, TiCl₃(TiCl₄To H₂Return
Original, reduced with Al metal, or organic gold
Including those reduced with a genus compound), TiBr₃, Ti
(OC₂H₅) Cl₂, TiCl₂, Dicyclopentadi
Use of titanium compounds such as enil titanium dichloride
Is also possible. [0010] Among these titanium compounds, tetravalent titanium
Compounds are preferred, especially TiCl₄, Ti (OC₄H
₉)₄, Ti (OC₂H₅) Cl₃Are preferred. Chita
As described above, tetravalent ones are preferable, but some of them are three-valent.
It may be less than the value. 4 trivalent titanium compounds
When manufacturing by reduction of a multivalent titanium compound,
Depending on the degree, such multivalent titanium compounds
Can be obtained. Halogen is the above magnesium and
(Or) is supplied from a halogen compound of titanium
Normal but other halogen sources, such as aluminum
Halides, halides of silicon, halogens of phosphorus
Can be supplied from known halogenating agents such as
Wear. Halogen contained in the catalyst component is
It can be hydrogen, chlorine, bromine, iodine or a mixture of these.
And chlorine is particularly preferred. [0013] Contains titanium, magnesium and halogen.
The solid component itself is known. For example, JP
No. 53-45688, No. 54-3894, No. 54-
Nos. 31092, 54-39483, 54-945
No. 91, No. 54-118484, No. 54-13158
No. 9, No. 55-75411, No. 55-90510,
No. 55-90511, No. 55-127405, No. 5
5-147507, 55-155003, 56
-18609, 56-70005, 56-72
No. 001, No. 56-86905, No. 56-90807
No. 56-155206, No. 57-3803, No.
Nos. 57-34103, 57-92007, 57-
No. 121003, No. 58-5309, No. 58-531
No. 0, No. 58-5311, No. 58-8706, No. 5
8-27732, 58-32604, 58-3
No. 2605, No. 58-67703, No. 58-1172
No. 06, No. 58-127708, No. 58-18370
No. 8, No. 58-183709, No. 59-149905
And those described in JP-A-59-149906.
Used. [0014] Further, as an essential component of the component (A) of the present invention,
All silicon compounds are represented by the following general formula:
is there. General formula R¹R² _3-nSi (OR³)_n (Where R¹Is a branched aliphatic hydrocarbon residue or alicyclic
The hydrocarbon residue is represented by R²Is hydrogen R¹Same or different from
Is represented by R³Represents a hydrocarbon residue, and n represents 1 ≦ n
A silicon compound represented by the following formula:
It is. The silicon compound is a compound of the formula
It goes without saying that a mixture of Where R¹Is a branched aliphatic hydrocarbon residue
In some cases, branching from the carbon atom adjacent to the silicon atom
Are preferred. The branching group in that case is alkyl
Group, cycloalkyl group or aryl group (for example,
Phenyl or methyl-substituted phenyl).
New More preferred R¹Is the charcoal adjacent to the silicon atom
An elementary atom, that is, the α-position carbon atom is a secondary or tertiary
Is a carbon atom. In particular, silicon atoms
It is preferred that the carbon atoms combined are tertiary. R¹Charcoal
The prime number is usually 3 to 20, preferably 4 to 10. R²Is R¹Same or different carbon number 1
-20, preferably 1-10, branched or linear saturated
It is usually a sum aliphatic hydrocarbon group. R³Is fat
Aliphatic hydrocarbon residue, preferably aliphatic having 1 to 10 carbon atoms
It is usually a hydrocarbon residue. Specific examples of the silicon compound usable in the present invention
Is as follows. (CH₃)₃CSi (CH₃)
(OCH₃)₂, (CH₃)₃CSi (CH (CH₃)
₂) (OCH₃)₂, (CH₃)₃CSi (CH₃)
(OC₂H₅)₂, (C₂H₅)₃CSi (CH₃)
(OCH₃)₂, (CH₃)₃CSi (C₂H₅) (O
CH₃)₂, (CH₃)₃CSi (n-C₃H₇) (O
CH₃)₂, (CH₃)₃CSi (i-C₄H₉) (O
CH₃)₂, (CH₃)₃CSi (C₅H₉) (OCH
₃)₂, (CH₃) (C₂H₅) CHSi (CH₃)
(OCH₃)₂, (CH₃)₃CSi (CH₃) (O-
nC₃H₈)₂, (CH₃)₃CSi (CH₃) (O-
nC₄H₉)₂, (CH₃)₃CSi (CH₃) (O-
nC₆H₁₃)₂, (CH₃)₃CSi (CH₃) (O-
nC₈H₁₇)₂, ((CH₃)₂CHCH₂)₂CSi
(OCH₃)₂, (C₂H₅) (CH₃)₂CSi (C
H₃) (OCH₃)₂, (C₂H₅) (CH₃)₂CS
i (CH₃) (OC₂H₅)₂, (CH₃)₃CSi
(OCH₃)₃, (CH₃)₃CSi (OC
₂H₅)₃, (C₂H₅)₃CSi (OC₂H₅)₃,
(CH₃) (C₂H₅) CHSi (OCH₃)₃, (C
H₃)₂CH (CH₃)₂CSi (CH₃) (OC
H₃)₂, ((CH₃)₃C)₂Si (OCH₃)₂,
(C₂H₅) (CH₃)₂CSi (OCH₃)₃, (C
₂H₅) (CH₃)₂CSi (OC₂H₅)₃, (CH
₃)₃CSi (O-tC₄H₉) (OCH₃)₂, (I
C₃H₇)₂Si (OCH₃)₂, (IC₃H₇)₂S
i (OC₂H₅)₂, (IC₄H₉)₂Si (OC
H₃)₂, (C₅H₉)₂Si (OCH₃)₂, (C₅
H₉)₂Si (OC₂H₅)₂, (C₅H₉) (C
H₃) Si (OCH₃)₂, (C₅H₉) (IC
₄H₉) Si (OCH₃)₂, (C₆H₁₁) Si (CH
₃) (OCH₃)₂, (C₆H₁₁)₂Si (OCH₃)
₂, (C₆H₁₁) (IC₄H₉) Si (OCH₃)₂,
(IC₄H₉) (SecC₄H₉) Si (OC
H₃)₂, (IC₄H₉) (IC₃H₇) Si (OC₅
H₁₁)₂, HC (CH₃)₂C (CH₃)₂Si (CH
₃) (OCH₃)₂, HC (CH₃)₂C (CH₃)₂
Si (OCH₃)₃, [0019] Embedded image [(CH₃)₃C] HSi (OCH₃)₂, [(C
H₃)₃C] HSi (OC₂H₅)₂, [(C₂H₅)
₃C] HSi (OCH₃)₂, (IC₃H₇) HSi
(OCH₃)₂, (IC₄H₉) HSi (OC
H₃)₂, (C₅H₉) HSi (OCH₃)₂, (C₅
H₉) HSi (OC₂H₅)₂, (C₆H₁₁) HSi
(OCH₃)₂, HC (CH₃)₂C (CH₃)₂Si
H (OCH₃)₂. The component (A) used in the present invention comprises the essential components described above.
In addition to the minute SiCl₄, CH₃SiCl₃Silicon compound such as
Object, (Al (O-iC₃H₇)₃, AlCl₃, AlB
r₃, Al (OC₂H₅)₃, Al (OCH₃)₂Cl
And B (OCH₃)₃, B
(OC₂H₅)₃, B (OC₆H₅)₃Boron compounds such as
Object, WCl₆, MoCl₅It is also possible to use other components such as
These are components such as silicon, aluminum and boron.
It may be left in the solid component as a part. Further, when producing this solid component,
Can be manufactured using electron donors as internal donors
it can. Electron donation usable for the production of this solid component
Alcohols, phenols as the body (internal donor)
, Ketones, aldehydes, carboxylic acids, organic acids
Or esters of inorganic acids, ethers, acid amides,
Oxygen-containing electron donors such as acid anhydrides, ammonia,
Oxygenated children like min, nitrile, isocyanate
Donors and the like can be exemplified. More specifically, methanol, ethanol
, Propanol, pentanol, hexanol, octane
Alcohols having 1 to 10 carbon atoms such as tanol and dodecanol
Coals, methyl formate, methyl acetate, ethyl acetate, acetic acid
Vinyl, propyl acetate, octyl acetate, cyclohexyl acetate
Sil, cellosolve acetate, ethyl propionate, methyl butyrate
, Ethyl valerate, ethyl stearate, chloroacetic acid
Chill, ethyl dichloroacetate, methyl methacrylate,
Ethyl tonate, ethyl cyclohexanecarboxylate, benzoate
Methyl benzoate, ethyl benzoate, propyl benzoate, benzoate
Butyl benzoate, octyl benzoate, cyclohexyl benzoate
Phenyl benzoate, benzyl benzoate, benzoic acid
Losolve, methyl toluate, ethyl toluate, tolu
Amyl ylate, ethyl ethyl benzoate, methyl anisate
, Ethyl anisate, ethyl ethoxybenzoate, phthalate
Diethyl phosphate, dibutyl phthalate, diheptyl phthalate,
γ-butyrolactone, α-valerolactone, coumarin,
Organics having 2 to 20 carbon atoms such as phthalide and ethylene carbonate
Acid esters, acetyl chloride, benzoyl chloride
Chloride, toluic acid chloride, anisic acid chloride, chloride lid
C2 to C15 such as royl, phthaloyl isochloride, etc.
Acid halides. Two or more of these electron donors may be used.
Can be. Of these, preferred are organic acid esters
And acid halides, with phthalic acid being particularly preferred.
Stele, cellosolve acetate and harai phthalate
Is. The component (A) of the present invention is required in addition to the essential components.
According to the above, it is possible to include optional components according to
There are, however, those suitable as such optional ingredients,
A vinyl silane compound can be mentioned. Specific examples of vinylsilane compounds include
Nosilane (SiH₄At least one hydrogen atom in
Vinyl group (CH₂ＣＨCH-) and the vinyl group
Is one or two, and the remaining hydrogen atoms are
Some of which are halogen (preferably Cl), alkyl
(Preferably having 1 to 12 carbon atoms), aryl (preferably
Or phenyl), etc.
(However, the vinylsilane compound and the component (ii) and
And (iii) do not have the same structure)
Typically, CH₂= CH-SiH₃, CH₂= CH-Si
H₂(CH₃), CH₂= CH-SiH (CH₃)₂,
CH₂= CH-Si (CH₃)₃, CH₂= CH-Si
Cl₃, CH₂= CH-SiCl₂(CH₃), CH₂
= CH-SiCl (CH₃) H, CH₂= CH-SiC
l (C₂H₅)₂, CH₂= CH-Si (C
₂H₅)₃, CH₂= CH-Si (CH₃) (C
₂H₅)₂, CH₂= CH-Si (C₆H₅) (C
H₃)₂, CH₂= CH-Si (CH₃)₂(C₆H₄
CH₃), (CH₂= CH) (CH₃)₂-Si-O-
Si (CH₃)₂(CH = CH₂), CH₂= CH-S
i (CH₃)₂(CH₂Cl) (CH₂= CH)₂SiCl₂, (CH₂= CH)₂S
i (CH₃)₂Etc. can be exemplified. these
Among them, vinylsilane containing no oxygen is preferred.Production of component (A) Component (A) of the present invention is used as long as the effects of the present invention are recognized.
It can be manufactured by any method. Typically
The following conditions are preferable. The contact temperature is -50 to 200
° C, preferably 0 to 100 ° C. Contact method and
Is a rotating ball mill, vibration mill, jet mill, medium
Mechanical method using a body agitator, etc.
In the presence, there is a method such as contacting by stirring
You. The inert diluent used at this time may be aliphatic or diluent.
Or aromatic and halogenated hydrocarbons,
Loxane and the like. In addition, an essential component used in the production of the component (A)
The effect of the present invention is confirmed by
Can be anything as long as possible, but in general the following
Within the range is preferred. First, titanium, magnesium and
For halogens, the amount of titanium compound used is
1 × 1 in molar ratio to the amount of magnesium compound used
0^-FourIt is good to be in the range of ~ 1000, preferably 0.01 ~
It is within the range of 10. Compounds therefor as halogen sources
When using the product, the amount used is titanium compound and
(Or) contains magnesium compound containing halogen
Regardless of whether or not magnesium is used,
And a molar ratio of 1 × 10^-2Good within the range of ~ 1000
More preferably, it is in the range of 0.1 to 100. Further, R¹R² _3-nSi (OR³)_nUse of
The dose is based on the amount of magnesium compound used.
1 × 10 in molar ratio^-FiveGood within the range of ~ 1000, preferred
Or in the range of 0.01 to 100. Further, it is used for producing the component (A).
The amount of the optional components used is preferably within the following ranges.
No. When an electron donating compound is used,
The dosage is based on the amount of magnesium compound used.
1 × 10^-3It is preferably in the range of 10 to 10, preferably
It is in the range of 0.01 to 5. Silicon, aluminum and boron compounds
The amount of use when using
1 × 10 in molar ratio to the amount of compound used^-3~ 100 range
The range is good, preferably within the range of 0.01 to 1. Use when using a vinylsilane compound
The amount is a molar ratio based on the amount of the magnesium compound used.
At 1 × 10^-3To 100, preferably in the range of 0.1 to 100.
It is in the range of 01-10. Component (A) comprises the above-mentioned titanium source, magnesium
Source, halogen source, silane source and electron if necessary
Using other components such as a donor, for example,
It is manufactured by the method. (A) Magnesium halide and titanium-containing compound
R¹R²Si (OR³)_3-nA silicon compound represented by
And electron donor and / or vinyl sila as required
A method of contacting the compound with a compound. (B) Halogenated phosphorus from alumina or magnesia
Treated with the compound, and magnesium halide, electric children
Giving, R¹R²Si (OR³)_3-nIncluding titanium halogen
A method of contacting an organic compound. (C) Magnesium halide and titanium tetra alcohol
Oxide and certain polymeric silicon compounds
The resulting solid component contains R¹R²Si (OR³)_{3- n},
Tan halogen compounds and / or silicon halogen
Compound and, if necessary, electron donor and / or vinyl
For contacting silane compounds and organometallic compounds
Law. The polymer silicon compound is represented by the following formula:
Is suitable. [0035] Embedded image (Where R⁶Is a hydrocarbon residue having about 1 to 10 carbon atoms,
q is the viscosity of the polymer silicon compound is 1 to 100 centimeters.
Demonstrates the degree of polymerization to be about Chistokes)
Means methyl hydrogen polysiloxane, ethyl high
Drogen polysiloxane, phenylhydrogenpo
Lisiloxane, cyclohexyl hydrogen polysilo
Xane, 1,3,5,7-tetramethylcyclotetracy
Loxane, 1,3,5,7,9-pentamethylcyclope
Preferred are n-siloxane and the like. (D) Titanium tetraalkoxy with magnesium compound
And an electron donor to form a halogenating agent or
Titanium is added to the solid component precipitated with titanium halide compound.
Compound, R¹R²Si (OR³)_3-nContact
Law. (E) Organic magnesium compounds such as Grignard reagents
After reacting with a halogenating agent, reducing agent, etc.
Depending on the electron donor R¹R²Si (OR³)_3-nAnd Chita
A method of contacting the compound with a compound. (F) Titanium compound to alkoxy magnesium compound
Thing, R¹R²Si (OR³)_3-nChildren if necessary
A method of contacting a donor with an organometallic compound. <Component (B)> The component (B) used in the present invention is as follows.
Organic consisting of the reaction product of component (i) and component (ii)
It is a metal compound component.Component (i) General formula [0036] Embedded image (Where R⁴Is a hydrocarbon residue having 1 to 10 carbon atoms)
Is an alkylboronic acid represented by the formula (R⁴Is the carbon number
Represents 1 to 10, preferably 1 to 6, hydrocarbon residues
). Specific examples of such alkylboronic acids include:
Methyl boronic acid, ethyl boronic acid, isopropyl boron
Acid, n-propylboronic acid, n-butylboronic acid, iso-
Butylboronic acid, n-hexylboronic acid, cyclohexyl
Ruboronic acid, phenylboronic acid, 3,5-difluorofur
Phenylboronic acid, pentafluorophenylboronic acid and
And 3,5-bis (trifluoromethyl) phenylboron
Acids, and the like. Preferred of these are:
Methylboronic acid, iso-butylboronic acid, 3,5-diflu
Orophenylboronic acid and pentafluorophenylbo
And the like. More preferred is methylboron
Is an acid.Ingredient (ii) Component (ii) is an organoaluminum compound. The component of the organoaluminum compound of the component (ii)
As an example, the general formula R⁷ _3-γAlX_γOr [0038] Embedded image Or [0039] Embedded image Some are represented by (However, R⁷Is carbon number 1 to 1
0 represents a hydrocarbon residue; X represents a hydrogen or a halogen group;
⁸Is hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, and γ is
0 ≦ γ <3, respectively. ) Specifically, (a)
Trimethyl aluminum, triethyl aluminum,
Liisobutyl aluminum, trihexyl aluminum
Aluminum, trioctyl aluminum, tridecyl aluminum
Tri-n-butylaluminum, tri-n-propyla
Trim such as luminium and triisoprenyl aluminum
Alkyl aluminum, (b) dimethyl aluminum
Chloride, diethylaluminum monochloride, diiso
Butyl aluminum monochloride, methyl aluminum
Musesquichloride, ethyl aluminum sesquichlori
Alkyl and ethyl aluminum dichloride
Luminium halide, (C) dimethyl aluminum high
Dried, diethylaluminum hydride, diiso
Alkyl aluminum such as butyl aluminum hydride
Hydride, (d) dimethyl aluminum (g)
Trimethylsiloxide), dimethyl aluminum (trim
Tylsiloxide), diethylaluminum (trimethyl)
Alkylaluminum siloxides such as siloxides),
(E) tetraisobutylalumoxane, tetraethyla
Examples include tetraalkylalumoxane such as lumoxane
Is done. It is also possible to use a mixture of two or more of these.
You. Of these organoaluminum compounds,
Preferred are trimethylaluminum, triisobu
Chill aluminum, dimethyl aluminum chloride, di
Isobutyl aluminum chloride, diisobutyl aluminum
Methyl aluminum and isobut
It is a derivative of chilled aluminum. More preferred
Means trimethylaluminum, triisobutylaluminum
And mixtures thereof.Contact between component (i) and component (ii) When the components (i) and (ii) are reacted, the use ratio is
Optionally, the desired reaction product can be efficiently produced.
To achieve this, the molar ratio of component (i) to component (ii) is 1:
Preferably, it is set to 2. In addition, component (i)
And the reaction of component (ii) are usually carried out under an inert gas atmosphere.
Performed in an inert solvent. There are various contact methods.
It is possible. For example, component (i) in (a) toluene solvent
, And then a diluted solution of component (ii) in toluene is added dropwise.
(Ii) Components of hexane dilution (ii)
A method of reacting by supplying component (i) as a solid in a solution
Method, (c) diluting component (i) and component (ii) in toluene
And then drop them into another container at a constant speed and react them.
Is exemplified. Reaction temperature between component (i) and component (ii);
The reaction time is optional, but generally it is a sudden reaction
Since both components are likely to occur, both components are kept at a low temperature, for example,
~ + 30 ° C, preferably after mixing at -78 to + 10 ° C,
A method in which the temperature is gradually increased, for example, -10 to + 70 ° C is preferred.
New The reaction time is limited as long as the desired product is obtained.
Is optional, but is generally in the range of 1 minute to 24 hours.
Be done. << Use of Catalyst / Polymerization >>Catalyst formation The catalyst according to the present invention connects component (A) and component (B).
It is formed by touching. Of the above component (B)
Any amount may be used as long as the effects of the present invention are recognized.
The component (B) / component (A) may be in a weight ratio of
0.1 to 1000, preferably in the range of 1 to 100
is there.polymerization The catalyst according to the present invention is applied to ordinary slurry polymerization
Of course, there is no liquid phase
It is also applicable to solvent polymerization, solution polymerization or gas phase polymerization.
For continuous polymerization, batch polymerization or pre-polymerization
It also applies to expressions. Used as a polymerization solvent for slurry polymerization
Hexane, heptane, pentane, cyclohexa
Saturated aliphatic or aromatic coal such as benzene, benzene, toluene
Hydrogen hydride may be used alone or in a mixture. The polymerization temperature is
Room temperature to about 300 ° C., preferably 50 to 200 ° C.
The polymerization pressure is atmospheric pressure to 300 kg / cm^TwoDegree, preferred
Is atmospheric pressure to 50 kg / cm^TwoAnd the molecular weight adjustment at that time
Hydrogen can be used as an auxiliary agent. Further, the stereoregularity of the obtained polymer is controlled.
A known ester as a third component during polymerization,
Use of electron-donating compounds such as ethers and amines
Can also. In the case of slurry polymerization, use of component (A)
Amount is 0.001-0.1 grams, component (A) / lit
The solvent range is preferred.Olefin The α-olefins polymerized by the catalyst system of the present invention have the general formula
R-CH = CH₂(Where R is a hydrogen atom or carbon number
1 to 10 hydrocarbon residues, which may have a branched group
No. ). Specifically, Echire
Propylene, butene-1, pentene-1, hexene
Olefins such as -1,4-methylpentene-1
You. Preferred are ethylene and propylene. This
In addition to homopolymerization of these α-olefins, copolymerization,
For example, ethylene and up to 50% by weight thereof, preferably 20%
To copolymerize with the above olefins up to
Of the above oleic acid up to 30% by weight with respect to propylene.
Can copolymerize with fins, especially ethylene
You. Other copolymerizable monomers (eg, vinyl acetate,
(A diolefin or the like). [0044] 【Example】 Example-1 [Production of component (A)] The internal volume of which was sufficiently replaced by nitrogen 0.4
A 1.6 mm inner diameter steel bo
Of anhydrous MgCl.₂20 grams,
(T-Bu) (n-Pr) Si (OMe)₂3.8m
LiLi, TiCl₄1.5 ml each
It was introduced and pulverized in an atmosphere of 20 ° C. for 48 hours. End of grinding
After completion, the pulverized material is removed from the mill, and the component (A)
It was a solid component. Then, 50 was replaced with nitrogen which had been sufficiently purified.
In a 0 ml flask, fully purified n-hep
100 ml of tan and 5 g of the above solid component
Introduces 2.5 ml of divinyldichlorosilane
And contacted at 30 ° C. for 2 hours. After contact, n-hep
It was sufficiently washed with a tan to obtain the component (A). To this one
As a result of composition analysis, titanium content = 2.3 wt.
%, (T-Bu) (n-Pr) Si (OMe)₂Content =
It was 9.5 wt%. [Production of component (B)] Bis (diisobutylaluminumoxy) methylboron
Was synthesized according to the following method. That is, 500 milliliters of nitrogen-substituted
Add fully dehydrated and deoxygenated n-hex
100 ml of sun and Aldrich
3.0 g (50 mmol) of tyl boric acid component (i)
Introduced. After cooling to -50 ° C or lower, triisobutyl
19.8 grams (100 mmol) of aluminum
(Ii) was diluted with 100 ml of n-hexane and 30
It was dripped slowly over a minute. -50 ℃ or less during dropping
The reaction temperature was maintained. After dropping, reach 0 ° C over 1 hour
The temperature gradually increased. Gas gradually rises around -10 ° C during heating
Occurred and the reaction proceeded. As the reaction progresses, the solid
The tyl boric acid dissolved. After keeping at 0 ° C for 2 hours,
Return to complete the reaction. After completion of the reaction, the solvent is distilled off under reduced pressure.
As a result, about 17 grams of the liquid compound (catalyst component
(B)) was obtained. [Polymerization of propylene] with stirring and temperature control device
1.5 liter stainless steel autoclave
500 n-heptane fully dehydrated and deoxygenated
Milliliter, bis prepared above as component (B)
(Diisobutylaluminumoxy) methylboron 20
0 milligrams and 15 milligrams of component (A) prepared above.
Regram, then introduce 60 ml of hydrogen and raise
Temperature rise and polymerization pressure = 7kg / cm^TwoG, polymerization temperature = 70
The polymerization of propylene was carried out under the conditions of
Was. After polymerization, the polymer slurry obtained is filtered.
More separated and the polymer was dried. As a result, 81.
4 grams of polymer were obtained. Also, 0.18 g of po
A rimmer was obtained. All products from boiling heptane extraction test
I. I (hereinafter abbreviated as TII) is 96.9% by weight.
there were. MFR = 1.6 g / 10 min, polymer bulk specific gravity =
0.43 g / cc. Also, the Q value (Mw
/ Mn), it was Q = 7.3. Example-2 [Production of Component (A)] In a flask sufficiently purged with nitrogen,
100 ml of dehydrated and deoxygenated n-heptane
And then MgCl 2₂0.1 mol and Ti
(O-nC₄H₉)₄At 95 ° C.
Allowed to react for hours. After completion of the reaction, the temperature was lowered to 35 ° C.
1,3,5,7-tetramethylcyclotetrasiloxane
15 ml was introduced and reacted for 5 hours. Generated
The solid component was washed with n-heptane. Then enough nitrogen
50 ml of n-heptane was added to the replaced flask.
And the solid component synthesized above was added in an amount of 0.1 mg in terms of Mg atoms.
03 mol was introduced. Then SiCl₄  0.06 mol
Introduced at 20 ° C for 30 minutes and reacted at 50 ° C for 3 hours
Was. After the completion of the reaction, the resultant is washed with n-heptane, and the component (A) is
It was a solid component for production. Titanium content in solid components
The amount was 4.52% by weight. Using this component,
1.0 milliliter of vinyltrimethylsilane
Tol, silicon compound (t-C₄H₉) (C
₂H₅) Si (OCH₃)₂1.2 ml and
And Al (C₆H₁₃)₃2.5 grams
Each was introduced and contacted at 90 ° C. for 2 hours. End of contact
Thereafter, the contact material is thoroughly washed with n-heptane to remove the component (A)
And When a part of the composition was analyzed and analyzed,
Content = 4.1 wt%, (t-C₄H₉) (C₂H₅)
Si (OCH₃)₂Content = 12.8 wt%. [Polymerization of propylene] Under the polymerization conditions of Example-1,
The amount of component (B) used was adjusted to 125 mg, and the polymerization temperature
The polymerization was carried out in exactly the same manner except that the temperature was changed to 75 ° C. 1
63.8 grams of polymer are obtained, MFR = 1.7 g
/ 10 min, TI. I = 97.9 wt%, polymer specific gravity
= 0.48 (g / cc), and the Q value was 7.8. Comparative Example-1 In the polymerization of Example 1, triisopropane was used as component (B).
Other than using 200 mg of butyl aluminum
Was polymerized in exactly the same manner. 85.6 grams of poly
Is obtained and T.I. I = 96.7 wt%, MFR =
2.1 g / 10 min, polymer bulk specific gravity = 0.44 g / cc
Q value was 4.7. Comparative Example-2 In the polymerization of Example 2, triethyl was used as the component (B).
All but 125 milligrams of aluminum
Polymerization was carried out in the same manner. 143.7 grams of polymer
Was obtained, MFR = 2.2 g / 10 min, T.I. I = 9
7.6 wt%, polymer bulk specific gravity = 0.47 g / cc
Q value was 4.5. Examples 3 to 7 In the polymerization of propylene in Example-2, component (B) and
Except that the contact product shown in Table 1 was used.
Polymerization was carried out in the same manner. The obtained results are shown in Table 1.
It was. [0048] [Table 1]Example-8 [Production of Component (A)] Substituted with sufficiently purified nitrogen 5
In a 00 ml flask, add Mg (OC₂H₅)₂
20 grams, 100 milliliters of purified toluene
And then TiCl₄60 ml, 70
Temperature rise to ℃ and introduce 8.6 ml of Cellsolve acetate
Then, the temperature was raised to 100 ° C. and reacted for 3 hours. End of reaction
Thereafter, it was thoroughly washed with n-heptane. Then, TiCl
₄  Introduce 100 ml and react at 110 ° C for 3 hours
I responded. After the reaction is completed, wash thoroughly with n-heptane.
Thus, a solid component for the component (A) was obtained. As in the synthesis of component (A) in Example-2,
100 milliliters of n-heptane in a fully purified flask
5 g of the above solid component, (t-B
u) (Me) Si (On-Pr)₂3.0 millilitres
, TiCl₄Into each 0.5 ml,
Contact at 25 ° C. for 2 hours, and after completion of contact, then AlEt
₂Introduce 1.4 grams of Cl and contact at 30 ° C for 1 hour
I let it. After the end of the contact, wash thoroughly with n-heptane,
Component (A) was used. As a result of the composition analysis of the component (A), Ti
Content = 3.1 wt%, (t-Bu) (Me) Si (On
-Pr)₂Content = 7.3 wt%. [Polymerization of propylene]
Was performed. 146.7 grams of polymer were obtained,
MFR = 1.9 (g / 10 min), T-I. I = 96.7 layers
%, Polymer bulk specific gravity = 0.39 (g / cc), Q value =
7.1. Example-9 [Production of component (A)] Remove into a flask which is sufficiently purged with nitrogen.
200 ml of water and deoxygenated n-heptane
And then MgCl₂0.4 mol, Ti (On
C₄H₉)₄And reacted at 95 ° C for 2 hours
I let it. After the reaction is completed, the temperature is lowered to 40 ° C.
Lehydropolysiloxane (20 centistoke
Was introduced and reacted for 3 hours. Raw
The solid component thus formed is washed with n-heptane,
did. Then, place the flask in a well-purged nitrogen flask.
Introduce 50 ml of n-heptane purified as described above.
And the solid component synthesized above was converted to 0.2 in terms of Mg atom.
4 moles were introduced. Then 25 ml of n-heptane
To SiCl₄  0.8 mol mixed at 30 ° C for 30 minutes
And the mixture was reacted at 90 ° C. for 1 hour. reaction
After completion, it was washed with n-heptane. Sufficient purification in a flask sufficiently purged with nitrogen
50 ml of n-heptane was introduced, and then
5 g of the solid component obtained above is introduced, and then the silicon compound
(CH₃)₃CSi (CH₃) (OCH₃)₂
Was introduced in an amount of 1.2 ml, and an optional component
Introducing 3.0 grams of chilled aluminum each, 3
Contact was made at 0 ° C. for 2 hours. Then, as an optional component,
Cl₄5.8 ml of the above silicon compound
1.6 ml and triethyl of the above optional ingredients
30 grams of aluminum, each introducing 3.0 grams
For 2 hours. After contact, n-heptane is sufficient
Then, the resultant was washed as Component (A). Take out a part
The content of the tan was determined to be 3.87% by weight. [Polymerization of propylene] with stirring and temperature control device
1.5 liter stainless steel autoclave
In addition, 50 dehydrated and deoxygenated n-paraffins
0 ml, component (B) bis (diisobutyl alcohol)
30 mg of miniumoxy) methylboron, above
Introduce 75 milligrams of each component (A),
The polymerization pressure is 9 kg / cm.^TwoG, polymerization temperature 200 ° C,
Polymerization was performed under the conditions of a polymerization time of 2 hours. After polymerization is completed,
The polymer solution treated with ethanol is
Separated from n-paraffin and dried to obtain a polymer.
The result was 83.6 grams of polymer, with an MFR
= 4.7 g / 10 min, Q = 9.3.

Claims (1)

(57) [Claim 1] An olefin polymerization catalyst comprising the following components (A) and (B): Component (A): titanium, magnesium, Ziegler type catalyst for the solid component _{^{R 1 R 2 3-n Si}} (OR 3) containing a halogen and an essential component a silicon compound represented by the general formula _n (wherein, R ¹ is a branched aliphatic hydrocarbon residue or an alicyclic hydrocarbon residue, R ² is a hydrocarbon residue which is the same as or different from R ¹ , R ³ is a hydrocarbon residue, and n is 1 ≦ n ≦ 3 Component (B): An organometallic compound component comprising the reaction product of the following components (i) to (ii). Component (i): General formula (Where R ⁴ has 1 to 1 carbon atoms)
0 hydrocarbon residues. ) Component (ii): Organoaluminum compound