JPS63308007A - Production of liquid alpha-olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a low-molecular liquid alpha-olefin polymer useful for cosmetic such as cream in high productivity, by using a highly active coordinated anionic catalyst comprising a Ti-supporting composition, an organoaluminum compound and an aluminoxanes. CONSTITUTION:6-12C alpha-olefin is polymerized in the presence of a catalyst consisting of (A) a Ti-supporting composition obtained by supporting a Ti compound (e.g. TiCl4 or tetrabutoxytitanium) on a metallic chloride (e.g. MgCl2 or CoCl2) as a transition metallic catalytic component and (B) an organoaluminum compound (e.g. trimethylaluminum or isobutylaluminum sesquichloride) and/or an aluminoxane [e.g. compound shown by formula I or formula II (R is 1-4C alkyl; n is 1-30) as an organoaluminum compound under conditions of molar ratio of Al/Ti>=100 and molar ratio of monomer/Ti<=2,000.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a liquid α-olefin polymer,
More specifically, the present invention relates to a method for producing a liquid α-olefin dipolymer with high production efficiency.

[Conventional technology]

Liquid α-olefin polymers are obtained by thermal polymerization, radical polymerization, cationic polymerization, or coordination anionic polymerization. However, liquid α-olefin polymers obtained by thermal polymerization have poor oxidative stability and are markedly colored, and radical polymerization and cationic polymerization using Friedelta raft catalysts can only yield highly viscous liquid α-olefin polymers. . In addition, cationic polymerization using a Lewis acid Lewis base complex catalyst can easily control and obtain molecular weights ranging from low to high molecular weights, but it has the problem of poor productivity.
Furthermore, although a liquid product with good oxidation stability can be obtained by coordination anionic polymerization using a Ziegler catalyst, there is a problem in that it is difficult to obtain a low molecular weight polymer.

Recently, by using Ziegler's catalyst together with co-catalysts such as alkaline total urine hydroxide, lithium or sodium metal, it has been used for applications such as synthetic lubricating oils and oil components of cosmetics.
Low viscosity liquid α-olefin polymers are being developed (Japanese Patent Application Laid-Open No. 113889-1989,
113890, etc.). Also, JP-A-61 2212
No. 0L discloses a method for producing a low-viscosity α-olefin polymer by copolymerizing an α-olefin in the presence of a catalyst consisting of a titanium or zirconium compound and an aluminoxane. However, these methods for producing polymers have the drawbacks of low catalyst activity and slow reaction rates.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a method for producing a liquid α-olefin polymer that can obtain a low molecular weight liquid α-olefin polymer in good yield using a highly active coordinating anion catalyst.

[Means for solving problems]

The present invention provides fa) a supported titanium composition in which a titanium compound is supported on a metal chloride as a transition metal catalyst component, and (b) Al in the presence of a catalyst consisting of an organoaluminum compound and/or aluminoxane as an organometallic compound component. It is characterized in that an α-olefin having 6 to 12 carbon atoms is polymerized under the following conditions: /Ti (molar ratio)≧100 and monomer/Ti (molar ratio)≦2,000.

The α-olefins having 6 to 12 carbon atoms used in the present invention include hexene-1, heptene-1, octene-1,
nonene-1, decene-1, undecene-1, dodecene-
Among them, hexene-1, octene-1, and decene-1 are particularly preferred. Two or more types of these may be used.

Examples of the metal chloride that is the (a) transition metal catalyst component used in the present invention include magnesium chloride, calcium chloride, cadmium chloride, ferrous chloride, cobalt chloride, nickel chloride, etc. Among these, chloride Magnesium, cobalt chloride, and nickel chloride are preferred, and magnesium chloride is particularly preferred.

Further, (a) titanium compounds supported on the metal chloride include titanium halides, haloalkoxytitanium, alkoxytitanium, etc., specifically titanium tetrachloride, titanium trichloride, triethoxytitanium chloride, tributoxytitanium chloride, etc. Particularly preferred are titanium, tetraethoxytitanium, and tetrabutoxytitanium.

When the titanium compound is not supported on the carrier, the activity is extremely low and the productivity is poor.

Examples of the organoaluminum compound that is the organometallic compound component (b) used in the present invention include trialkylaluminum, dialkylaluminum monochloride, alkylaluminum sesquichloride, alkylaluminum dichloride, and specifically, trimethylaluminum, triethylaluminum, and the like. Examples include aluminum, triisobutylaluminum, diethylaluminium monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, and the like.

In addition, as aluminoxane, the general formula % formula % (in the formula, R is an alkyl group having 1 to 4 carbon atoms, and n is 1 to 30
(representing a number), specific examples include methylaluminoxane and ethylaluminoxane.

In the present invention (when preparing a supported titanium composition which is an al transition metal catalyst component), the molar ratio of titanium compound to metal chloride is set to 0.02 to 4.
0, especially preferably 0.1 to 2.0. If the molar ratio is too small, the amount of metal chloride relative to the titanium compound will be too large, resulting in low polymerization activity (g-catalyst light), and If it is too high, the carrier effect of the metal chloride on the titanium compound will not be sufficiently exerted, and the polymerization activity (per g - Ti) will decrease.
becomes lower.

In addition, in the present invention, by mixing an electron donating compound during the preparation of the (al transition metal catalyst component),
It can be activated. Examples of the electron donating compound include JP-A-48-16986 and JP-A-50-1265.
Compounds shown in JP-A No. 90 and JP-A-52-151691, such as esters of aromatic carboxylic acids and esters of aliphatic carboxylic acids, can be used, and among these, ethyl benzoate is particularly preferred.

Furthermore, in the present invention, after preparing the above-mentioned (al transition metal catalyst component), it is also possible to bring the above-mentioned organoaluminum compound into contact with it for preliminary reduction.

The amount of the organoaluminum compound and/or aluminoxane used in the present invention needs to be 100 or more, preferably 200 or more in terms of Al/T i (molar ratio). When the molar ratio of A 1 /Ti is less than 100, satisfactory polymerization activity cannot be obtained and the molecular weight of the obtained polymer becomes high.

In addition, in the present invention, the monomer/Ti molar ratio is 2,
It is necessary to carry out the polymerization at a molecular weight of 000 or less. When the molar ratio exceeds 2,000, the molecular weight of the resulting polymer becomes high.

The polymerization temperature when producing the liquid α-olefin polymer of the present invention is 0 to 150°C, preferably 10 to 100°C, and the polymerization pressure is 0 to 50 kg/csf (gauge pressure), preferably 0 to 20 kg/co ((gauge pressure), polymerization time is 5
minutes to 3 hours, preferably IO minutes to 2 hours.

Further, in producing the polymer of the present invention, hydrogen gas and a dialkylzinc compound can be used for the purpose of further lowering the molecular weight.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. In the examples, parts and % mean parts by weight and % by weight unless otherwise specified.

In addition, the number average molecular weight in terms of polystyrene in the Examples was measured as follows according to the method described in "Gel Permeation Chromatograph" (written by Takeuchi, published by Maruzen Co., Ltd.).

First, using standard polystyrene with a known molecular weight (manufactured by Toyo Soda Co., Ltd., monodisperse polystyrene), the molecules (IM and its G
PC (gel permeation chromatography) counts were measured, and molecular IM and EV (Elution Vol.
A correlation diagram calibration curve of the amount of eluent) was drawn, and then the GPC pattern of the sample was measured by the standard method, and the molecular weight M was determined using the calibration curve. The sample preparation conditions and GPC measurement conditions at that time are as follows.

A) Sample preparation 0-Dichlorobenzene solvent with 2.6- as anti-aging agent
Adding 0.08% di-t-butyl-p-cresol,
After dissolving, the sample was separated with 0-dichlorobenzene solvent to a concentration of 0.1%, heated to 135°C, and heated to about 6
Dissolve for 0 minutes and apply to GPC. Note that in the GPC device, filtration is automatically performed using a 0.5 μm sintered filter.

B) GPC measurement conditions Equipment: Manufactured by Waters, USA Model 150 column: Manufactured by Toyo Soda Co., Ltd. I] Type Sample amount = 500 μl Temperature: 135°C Flow rate: 1 m 17 minutes Column theoretical plate number: 1 x 104 ~ 2 x 10' (measured value with acetone) Examples 1 a) Catalyst preparation In a stainless steel ball mill that had been purged with nitrogen in advance, 210 mmol of magnesium chloride and 1 mol of tetrabutoxytitanium were added.
05 mmol and 64 ml of n-hexane were charged, and the mixture was ground in a vibration mill at room temperature for 7 hours. After pulverization, the entire contents were taken out and washed five times with 400 ml of n-hexane, then 400 ml of n-hexane was charged, and while stirring at room temperature, 1 mol/1 liter of diethylaluminum monochloride was added.
0.5 mmol was added dropwise to the mixture, and the mixture was reacted at room temperature for 5 hours.

After washing the obtained reaction solution five times with 400 ml of n-hexane, 400 mj+ of n-hexane was added to prepare a supported titanium catalyst slurry. The titanium concentration of this supported titanium catalyst slurry was 0.04 mol/l.

b) 50ml of dehydrated toluene was added to a 200ml flask which had been previously purged with nitrogen.
Reagent grade) 3 ml (0,028 mol), supported titanium catalyst prepared with methylaluminoxane (Toyo Stouffer Chemi 1000 mmol (as AZ) and a) 0
．． 04 mmol (as Ti) was charged, and polymerization was carried out at 40°C for 1 hour (the molar ratio of A j2 / Ti was 2
5,000, and the monomer/Ti molar ratio is 700). After the polymerization reaction was terminated, the polymerization solution was concentrated to obtain 1.2 g of a liquid polymer. The polymerization activity of the obtained polymer was 630g polymer/
g-Ti・h, polystyrene equivalent number average molecular weight is 6.0
It was 00.

Example 2 a) Catalyst Preparation In a stainless steel ball mill purged with nitrogen in advance, 100 mmol of magnesium chloride, 7.5 mmol of ethyl benzoate, 15 mmol of titanium tetrachloride, and 64 mmol of n-hexane were added.
ml was charged and ground in a vibrating mill at room temperature for 7 hours. After crushing, take out the entire contents and add 400 mj of n-hexane.
! After washing with water five times, 700 m6 of n-hexane was added to prepare a supported titanium catalyst slurry. The titanium concentration of this supported titanium catalyst slurry was 0.02 mol/1.

b) In Polymerization Example 1b), the solvent was changed from toluene to n-hexane, and the monomer ' was changed from hexene-1 to decene-1 (0,0
1588 mol), 1000 mmol of methylaluminoxane to 5 mmol of triisobutylaluminum (A1
), and the supported titanium catalyst obtained in a) was changed to 0.
Polymerization was carried out at 30°C for 30 minutes using 01 mmol (as Ti) to obtain a liquid polymer (Aj!/Ti molar ratio was 500
, monomer/Ti molar ratio 1,5°88). Obtained
The yield of the polymer was 2.0 g, the polymerization activity was 8,350 g polymer/g-Ti-h, and the number average molecular weight in terms of polystyrene was 5.200.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 2, except that the monomer was changed to hexene-1 and triisobutylaluminum was changed to 0.5 mmol (as AN) (A1/Ti mol). ratio is 50, monomer/Ti molar ratio is 2,800), the yield of the obtained polymer is 2.0 g,
The polymerization activity was 8.350 g polymer/g-rt-h, but because the Al/Ti ratio was too small, the product was not liquid but semi-solid, and the number average molecular weight in terms of polystyrene was 50°000. Ta.

Example 3 In Example 1, the supported titanium catalyst was replaced with the catalyst 0 of Example 2.
．． Polymerization was carried out in the same manner as in Example 1 except that methylaluminoxane was changed to 02 mmol (as Ti) and 700 mmol (as Al) (A1/Ti molar ratio was 35,000, monomer/Ti molar ratio is 1,40
0). The yield of the obtained liquid polymer was 1.1 g, the polymerization activity was 1.150 g polymer/g-Ti-h, and the number average molecular weight in terms of polystyrene was 8,200.

Comparative Example 2 In Example 2, 110 mJ of hexene was added to
Example 2 except that triisobutylaluminum was changed to 2 mmol (as Al) and triisobutylaluminum was changed to (0,0935 mol).
Polymerization was carried out in the same manner as (AA'/TiA1/Ti
The molar ratio monomer/Ti molar ratio is 9,350). The yield of the obtained polymer was 3.3 g, and the polymerization activity was 13,900 g polymer/g-Ti·h, but because the monomer/TI was too large, the product was not liquid but semisolid. ,
The number average molecular weight in terms of polystyrene was 40,000.

〔Effect of the invention〕

According to the present invention, a low molecular weight liquid α-olefin polymer having a number average molecular weight of 10.000 or less can be obtained in good yield. Further, the catalyst system in the present invention has a fast reaction rate, high activity, and high production efficiency.

The liquid α-olefin polymer obtained by the present invention can be used in synthetic lubricating oils such as grease base oil, gear oil, compressor oil, turbine oil, refrigeration oil, and electrical insulation oil, as well as in cold cream and cleansing cream. , creams such as vanishing creams, various emulsions, hair cosmetics such as hair creams, pomades, and ticks, Jump・
- It is useful for cosmetic applications as an oil component in cosmetic products such as rinses, medicated cream ointments, suppository bases, and other pharmaceutical products.

[Brief explanation of drawings]

FIG. 1 is a flowchart 1 of the method for producing a liquid α-olefin polymer of the present invention. Agent Patent Attorney Takeshi Kawakita Written Amendment to Long Procedures 1. Indication of the case 1986 Patent Application No. 143908 2 Name of the invention Process for producing liquid α-olefin polymer 3 Person making the amendment Relationship to the case Patent applicant address 2-11 Tsukiji, Chuo-ku, Tokyo No. 24 name
(417) Ryu Asakura, Representative of Japan Synthetic Rubber Co., Ltd.
Husband 4, Agent Address: 11-8-5, Kayabacho-Chome, Nihonbashi, Chuo-ku, Tokyo
, Date of amendment order Voluntary 6, Subject of amendment Detailed explanation of the invention in the specification. 7. Contents of the amendment (1) [ was on page 11, line 11 of the specification. ] before ", Mw/Mn (weight average molecular weight/number average molecular weight) =
5. Insert 2J. (2) Insert r, Mw/Mn=8.7J in front of j on page 12 of the specification, line 5 from the bottom. Insert ", M w / M n = 9.8 J" before "was.". (4) Insert r, Mw / before "was." on the fourth line from the bottom of No. Insert Mn=5.8J. (5) Insert r゛, M w / M n = 8.8 J after '40,0OOJO on page 14, line 8 of the specification. (6) The following statement is inserted after the 9th line of page 14 of the specification. Comparative Example 3 In Example 1, hexene-1 was added to 5.35 m e (
0,044 mol), supported Ti catalyst THC-32A (manufactured by Toho Titanio Co., Ltd.) 0.025 mmol (as Ti),
Methylaluminoxane 12.5 mmol (as Af)
was charged and polymerized for 30 minutes at 30°C (Al/Ti molar ratio 500, monomer/Ti molar ratio 1,760). The yield of the polymer was 1.15 g, the polymerization activity was 1.920 g polymer/g-Ti-h, and the number average molecular weight in terms of polystyrene was 18,000. Mw/Mn=5.9. . 1 or more

Claims (1)

[Claims] (1) In the presence of (a) a supported titanium composition in which a titanium compound is supported on a metal chloride as a transition metal catalyst component, and (b) a catalyst consisting of an organoaluminum compound and/or aluminoxane as an organometallic compound component, Al A method for producing a liquid α-olefin polymer, which comprises polymerizing an α-olefin having 6 to 12 carbon atoms under the following conditions: /Ti (molar ratio)≧100 and monomer/Ti (molar ratio)≦2,000.