JPH06821B2 - Liquid ethylene random copolymer and its use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a liquid ethylene random copolymer and its use as a synthetic lubricating oil. More specifically, it relates to a liquid ethylene-based random copolymer having a narrow molecular weight distribution and composition distribution and its use as a lubricating oil.

[Conventional technology]

Conventionally, liquid ethylene / propylene copolymers are expected to be used as synthetic lubricants or modifiers for various resins. As a production method thereof, a method is known in which ethylene and α-olefin are copolymerized in the presence of a titanium catalyst composed of a titanium compound and an organoaluminum compound or a vanadium catalyst composed of a vanadium compound and an organoaluminum compound. The liquid ethylene / α-olefin copolymer obtained by the titanium-based catalyst is generally inferior in random copolymer property, has a wide molecular weight distribution and composition, and is inferior in performance as a synthetic lubricating oil. Liquid ethylene / α-olefin copolymer obtained with vanadium catalyst has improved random copolymerizability compared to that obtained with titanium catalyst, narrows molecular weight distribution and composition distribution, and has performance as a synthetic lubricating oil. Is considerably improved, but quality improvement is still desired for applications requiring severe performance.

Regarding the ethylene / α-olefin copolymer using a vanadium catalyst, JP-B-47-21650, JP-A-57-117585, and JP-A-51-11280.
No. 9, Japanese Patent Publication No. 47-42723, Japanese Patent Laid-Open No. 48-
It is proposed in Japanese Patent No. 65205 and Japanese Patent Laid-Open No. 60-35009. Of these, Japanese Patent Publication No. 47-
No. 21650 and Japanese Patent Application Laid-Open No. 57-117585 describe the use of a liquid ethylene / α-olefin copolymer as a synthetic lubricating oil, the performance of which is as described above. It was Further, in JP-A-51-112809, a viscosity index improver comprising an ethylene-propylene copolymer having an n / n of 2.5 and [η] of 0.4 to 1.5 is started. The ethylene / propylene copolymers specifically described in the Reference Examples and Examples of the publication are all in the same form, and are described in JP-B-47-42723 and JP-A-48-65205.
The publication discloses that the lubricating oil has a crystallinity of 3 to 18%, w / n
A lubricating oil composition containing a solid ethylene / α-olefin copolymer having a ratio of 4 or less is described, but any of these solid ethylene / α-olefin copolymers can be used as a synthetic lubricating oil by itself. You cannot do it. Also,
In JP-A-60-35009, the w / n is 2
And a weight average molecular weight (w) of about 2000 to
Disclosed is an ethylene / α-olefin copolymer in the range of about 12,000,000, preferably about 10,000 to about 1,000,000, a lubricating oil formulation comprising a lubricating oil base and the ethylene / α-olefin copolymer. The ethylene / α-olefin copolymers specifically described in the examples of the publications are all high molecular weight solid copolymers, and these solid ethylene / α-olefin copolymers are the same as those mentioned above. As described above, neither of them can be used alone as a synthetic lubricating oil.

On the other hand, no description of a catalyst comprising a zirconium compound and aluminoxane as a new Ziegler-type olefin polymerization catalyst suggesting a liquid ethylene / α-olefin copolymer is found in the following series of prior art documents.

JP-A-58-19309 discloses that the following formula (cyclopentadienyl) ₂ M ₆ RHal, where R is cyclopetanedienyl, C ₁ -C ₆ -alkyl, halogen, and Me is a transition metal. Yes, Hal
Is a halogen, and a transition metal-containing compound represented by the following formula: Al ₂ OR ₄ (Al (R) -O) _n, wherein R is methyl or ethyl, and n is a number of 4 to 20, Or a linear aluminoxane represented by the following formula (Al (R) -O) _{n + 2,} wherein R and n are the same as defined above, in the presence of a catalyst consisting of a cyclic aluminoxane represented by: And a method of polymerizing one or more C _{6 to} C ₁₂ α-olefins at a temperature of −50 ° C. to 200 ° C. The publication describes that in order to control the density of the polyethylene obtained, the polymerization of ethylene should be carried out in the presence of small amounts of up to 10% by weight of some longer chain alpha olefins or mixtures.

JP-A-59-95292 discloses the following formula Here, n is 2 to 40 and is C _{1 to} C ₈ alkyl, and a linear aluminoxane represented by: Here, the definition of n and R is the same as above, and the invention relating to the method for producing a cyclic aluminoxane represented by is described. In this publication, for example, when methylaminoxane produced by the same production method is mixed with a titanium or zircon pis (cyclopentadienyl) compound, and olefin is polymerized, per 1 g of transition metal and for 1 hour. It is stated that 25 million g or more of polyethylene can be obtained.

Japanese Unexamined Patent Publication No. Sho 60-35005 discloses the following formula Wherein R ¹ is C ₁₀ alkyl, R ⁰ is R ¹ or is bonded to represent —O—, and the aluminoxane compound represented by is first reacted with a magnesium compound and then the reaction product is chlorinated. And Ti, V, Zr or C
A method for producing a polymerization catalyst for olefin by treating with a compound of r is disclosed. The same publication describes that the catalyst is particularly suitable for the copolymerization of a mixture of ethylene and C ₃ -C ₁₂ α-olefin.

Japanese Unexamined Patent Publication (Kokai) No. 60-35,006 discloses mono-, di- or tri-cyclopentadienyl of two or more different transition metals or its derivative (a) as a catalyst system for producing a reactor blend polymer. Alumoxane (aluminoxane) (b)
Are disclosed. In Example 1 of the publication, ethylene and propylene are polymerized with bis (pentamethylcyclopentadienyl) zirconium dimethyl as a catalyst and alumoxane as a catalyst to give a polyethylene having a number average molecular weight of 15,300 and a weight average molecular weight of 36,400 and a propylene component of 3.4%. What has been obtained is disclosed. In addition, Example 2
Then, ethylene and propylene were polymerized using bis (pentaethylcyclopentadienyl) zirconium difluoride, bis (methylcyclopentadienyl) zirconium diflloyde and alumoxane as catalysts to obtain a number average molecular weight of 2,
200, a weight average molecular weight of 11,900 and a number average molecular weight of 2,000 and a toluene soluble portion containing a propylene component of 30% and a number average molecular weight of 3,000, a number average molecular weight of 7,400 and a toluene insoluble portion containing a propylene component of 4.8 mol%. A blend of polyethylene and ethylene-propylene copolymer containing 8,300 and 7.1 mol% of propylene component is obtained. Similarly, the molecular weight distribution (w
/ N) an ethylene-propylene copolymer blend of LLDPE consisting of 4.57 and a soluble portion of 20.6 mol% propylene component and a molecular weight distribution of 3.04 and an insoluble portion of 2.9 mol% propylene component is described.

JP-A-60-35007 discloses that ethylene alone or together with α-olefin having 3 or more carbon atoms, a metallocene and the following formula (R-Al-O) _n, wherein R is an alkyl group having 1 to 5 carbon atoms. Is a group, and n is 1
A cyclic alumoxane represented by: or a formula R (R-Al-O) _n AlR ₂ wherein R and n have the same definitions as above, and a linear alumoxane represented by A method of polymerizing in the presence of a catalyst system is described. According to the description of the publication, the polymer obtained by the method is about 500 to about 1.
It has a weight average molecular weight of 400,000 and a molecular weight distribution of 1.5 to 4.0.

Further, Japanese Patent Laid-Open No. 60-35008 discloses at least 2
By using a catalyst system comprising a seed of a metallocene and alumoxane, copolymers of α- olefins polyethylene or ethylene and C ₃ -C ₁₀ having a width wider molecular weight distribution is described to be manufactured. The publication describes that the copolymer has a molecular weight distribution (w / n) of 2 to 50.

[Problems to be solved by the invention]

An object of the present invention is to provide a novel liquid ethylene random copolymer.

Another object of the present invention is to provide a liquid ethylene-based random copolymer having a narrow molecular weight distribution and a narrow compositional distribution.

Still another object of the present invention is to provide a liquid ethylene-based random copolymer having a high viscosity index and a high flash point and a low pour point.

Still another object of the present invention is to provide a liquid ethylene-based random copolymer which is excellent in shear stability, oxidation stability and thermal stability and which also has excellent molten metal film strength.

Still another object of the present invention is to provide a synthetic lubricating oil which is suitable as a lubricating oil and comprises the liquid ethylene random copolymer having the above excellent properties.

Still another object of the present invention is to provide a liquid ethylene-based random copolymer useful as a lubricating oil additive, a fuel oil additive or a modifier for a polyolefin, a rubbery polymer and the like in addition to a synthetic lubricating oil. It is in.

Still another object of the present invention is to provide a liquid ethylene-based random copolymer having a double bond capable of reacting with maleic anhydride or the like at the molecular terminal and therefore easily modified according to the purpose of each species. It is in.

Further objects and advantages of the present invention will be apparent from the following description.

[Means and Actions for Solving Problems]

Such an object and advantage of the present invention are, according to the present invention, a liquid ethylene-based random copolymer of ethylene and α-olefin having 3 to 10 carbon atoms, wherein (a) the content of the ethylene component is 10%. Is in the range of ~ 85 mol% and the content of α-olefin component is 15 ~ 90.
Mol% range, (b) gel permeation chromatography (GP
The number average molecular weight ( _n ) measured in C) is 3 × 10 ² to 1
In the range of × 10 ^4, (c) GPC in determined molecular weight distribution _{(w / n)} is not less than 2.5, (d) the following formula (1) [In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the α-olefin component, and P _OE represents the α-olefin / ethylene chain of the entire dyad chain. The B value represented by the following formula (II) is in a range satisfying the following formula (II) 1.05 ≦ B ≦ 2 (II), and (e) ¹³ C-NMP spectrum has The αβ and βγ signals based on the methylene chain between two adjacent tertiary carbon atoms in the combined main chain are not observed. And (f) the liquid ethylene random copolymer characterized in that the iodine value is in the range of 0 to 85.

The liquid ethylene-based random copolymer of the present invention is obtained by using ethylene and carbon in the presence of (A) a zirconium hydride compound having a group having a conjugated π electron as a ligand, and (B) an aluminoxane. Number of atoms 3 to 1
It can be produced by a method of copolymerizing 0 α-olefin.

The zirconium hydride compound (A) having a group having the conjugated π-electron as a ligand has, for example, the following formula (III) R ¹ R ² R ³ ZrH (III) where R ¹ is a cycloalkadienyl group. R ² and R ³ are cycloalkadienyl group, aryl group, alkyl group, halogen atom or hydrogen atom.

The cycloalkadienyl group is, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group or the like.

Examples of the alkyl group of R ² and R ³ include a methyl group,
Examples thereof include an ethyl group, a propyl group, an isopropyl group, and a butyl group.Examples of the aryl group include a phenyl group, a benzyl group, and a neofoyl group, and examples of the halogen atom include fluorine, chlorine, and chlorine. Examples thereof include bromine. The following compounds can be illustrated as the zirconium hydride compound.

Bis (cyclopentadienyl) zirconium monochloride monohydride, Bis (cyclopentadienyl) zirconium monobromide monohydride, Bis (cyclopentadienyl) methylzirconium hydride, Bis (cyclopentadienyl) ethylzirconium hydride, Bis ( Cyclopentadienyl) cyclohexyl zirconium hydride, Bis (cyclopentadienyl) phenyl zirconium hydride, Bis (cyclopentadienyl) benzyl zirconium hydride, Bis (cyclopentadienyl) neopentyl zirconium hydride, Bis (methylcyclopentadi) (Enyl) zirconium monochloride monohydride, bisindenyl zirconium monochloride monohydride.

The zirconium hydride compound may be used as it is, but a compound such as bis (cyclopentadienyl) zirconium monochloride monohydride which is poorly soluble in a solvent such as toluene should be used after contacting with an organoaluminum compound. Is preferred. By this operation, the solvent-insoluble zirconium hydride compound can be made easily soluble in the solvent.

Specific examples of the organoaluminum compound to be contacted with the zirconium hydride compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, and tributylaluminum, trialkenylaluminums such as triisoprenylaluminum, dimethylaluminum methoxide, and diethylaluminum ethoxide. In addition to dialkylaluminum alkoxides such as dibutylaluminum butoxide, alkylaluminum sesquimethoxide and alkylaluminum sesquiethoxide such as ethylaluminum sesquiethoxide, a partial composition having an average composition represented by R ¹ _2.5 Al (OR ² ) 0.5, etc. Alkoxy aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, dimethy Partially halogenated dialkyl aluminum hydrides such as aluminum bromide, alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, alkyl aluminum dihalides such as methyl aluminum dichloride and ethyl aluminum dichloride. The alkyl aluminum etc. which were mentioned can be illustrated.

The reaction of both compounds is preferably carried out in a hydrocarbon medium with or without light, and the mixing molar day (Al / Zr) of the organoaluminum compound and the zirconium compound is 0.5 to 30, preferably 1 to 20, and zirconium is used. The concentration of is 0.001 to 1 mol per liquid phase, preferably 0.005 to
The reaction temperature may be 0 to 120 ° C., preferably 20 to 100 ° C., and the both may be brought into contact with each other. The hydrocarbon medium can be selected from those exemplified as the solvent for polymerization described later.

Specific examples of the aluminoxane (B) as a catalyst constituent used in the above method include those represented by the general formula (IV) or the general formula
(V) (In the formula, R represents a hydrocarbon, m is preferably an integer of 20 or more, and particularly preferably an integer of 25 or more). In the aluminoxane, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group, and m is preferably 20 or more, Particularly preferred is an integer of 25 or more, and particularly preferred is an integer in the range of 30 to 100. The following method can be exemplified as a method for producing the aluminoxane.

(1) Compounds containing adsorbed water, salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate,
A method in which triacryl aluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate and reacted.

(2) A method in which water is allowed to directly act on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Of these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of organic metal component.

In the above method, the raw material supplied to the polymerization reaction system is a mixture of ethylene and α-olefin having 3 to 10 carbon atoms other than ethylene. The content of ethylene in the polymerization raw material olefin is usually 2 to 60 mol%, preferably 4 to 55 mol%, and the content of the α-olefin is usually 40 to 98 mol%, preferably 45 to 96 mol%. It is a range.

As the α-olefin having 3 to 10 carbon atoms other than ethylene used as a polymerization raw material in the above method, specifically, propylene, 1-butene, 1-hexene, 4-methyl-
Examples include 1-pentene, 1-octene, 1-decene and the like.

In the above method, the olefin polymerization reaction is usually carried out in a hydrocarbon medium. Specific examples of the hydrocarbon medium include butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane, and other alicyclic groups. In addition to hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, petroleum fractions such as gasoline, kerosene, and light oil, olefin as a raw material also serves as a hydrocarbon medium. Of these hydrocarbon media, aromatic hydrocarbons are preferred.

In the above method, the temperature during the polymerization reaction is in the range of -50 to 200 ° C, preferably -30 to 100 ° C, particularly preferably -20 to 80 ° C.

The ratio of the zirconium hydride compound (A) used in carrying out the above method is usually 10 ^-8 to 10 ^-2 gram atom /, preferably 10 ^-7 to 10 as the concentration of zirconium metal atom in the polymerization reaction system. It is in the range of 10 ⁻³ gram atom /. The proportion of aluminoxane used is usually 10 ^-4 to 10 ^-1 gram atom /, preferably 10 ^-3 , as the concentration of aluminum atoms in the polymerization reaction system.
To 5 × 10 ^-2 gram atom / g, and the ratio of aluminium metal atom to zirconium metal atom in the polymerization reaction system is usually 25 to 10 ⁷ , preferably 10 ² to 10 ⁶ . The molecular weight of the copolymer can be adjusted by hydrogen and / or the polymerization temperature.

In the above method, a liquid ethylene random copolymer having a high iodine value can be obtained by carrying out the copolymerization reaction in the absence of hydrogen, and a liquid ethylene random copolymer having a low iodine value can be obtained by carrying out the reaction in the presence of hydrogen. Copolymer or iodine value is 0
The liquid ethylene-based random copolymer can be obtained.

In the above-mentioned method, the liquid ethylene random copolymer of the present invention can be obtained by treating the polymerization reaction mixture in which the polymerization reaction is completed by a conventional method.

Further, the liquid ethylene random copolymer having a high iodine value obtained by the above method is hydrogenated in the presence of a hydrogenation catalyst according to a conventional method to obtain a liquid ethylene random copolymer having a lower iodine value. A liquid ethylene-based random copolymer having an iodine value or an iodine value of 0 can be obtained. As the hydrogenation catalyst, Group VIII metals such as iron, cobalt, nickel, rhodium, palladium and platinum can be used.
Of these, nickel, especially Raney nickel is preferred. Further, the hydrogenation reaction can be carried out in the presence of a solvent or in the absence of a solvent. Solvents include pentane, hexane, heptane, octane,
Hydrocarbons such as decane, cyclohexane, methylcyclohexane, and cyclooctane can be exemplified. The temperature during the hydrogenation reaction is, for example, 50 to 250 ° C,
It is preferably 100 to 200 ° C. The pressure during the hydrogenation reaction is, for example, in the range of 5 to 100 kg / cm ² -G.

The liquid ethylene-based random copolymer of the present invention is a transparent liquid copolymer at 25 ° C.

The composition of the liquid ethylene random copolymer of the present invention is such that the ethylene component is 10 to 85 mol%, preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%, and the α-olefin component is 15 to 90 mol%. %, Preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%.

The molecular weight distribution (M _w / M _n ) of the liquid ethylene random copolymer of the present invention measured by gel permeation chromatography (GPC) is 2.5 or less, preferably 2.2 or less, and particularly preferably 2 or less. Is the range.
If the molecular weight distribution of the liquid ethylene-based copolymer is larger than 2.5, it has a drawback that the flash point is low and the pour point is high when compared with those having the same molecular weight. The _w / _n value is measured according to "Gel Permeation Chromatography," published by Maruzen by Takeuchi.

(1) Using standard polystyrene of known molecular weight (Toyo Soda (manufactured by Toyo Soda Co., Ltd.) fractional polystyrene), the molecular weight M and its GPC (Gel Permeaion Chromatograph) count were measured, and the correlation diagram between the molecular weight M and EV (Elution Vollume) was calibrated. Create a curve. The concentration at this time is 0.02 wt%.

(2) A GPC chromatograph of the sample is taken by GPC measurement, and the polystyrene-equivalent number average molecular weight is determined by (1) above.
_{The n} weight average molecular weight _w is calculated and the _w / _n value is determined. The sample preparation conditions and GPC measurement conditions in that case are as follows.

[Sample preparation]

(A) The sample is dispensed into an Erlenmeyer flask together with an o-dichlorobenzene solvent so as to be 0.1 wt%.

(B) The anti-aging material 2, in the Erlenmeyer flask contained in the sample
6-di-tert-butyl-p-cresol is added at 0.05 wt% with respect to the polymer solution.

(C) The Erlenmeyer flask is heated to 140 ° C. and stirred for about 30 minutes to dissolve it.

(D) Pour the liquid on GPC.

[GPC measurement conditions]

 It carried out on the following conditions.

(A) Equipment Waters (150C-ALG / GP
C) (b) Column made by Dupont (ZORBAXPSM BiM odal
-S) (C) Sample amount 200 μ (D) Temperature 140 ° C. (V) Flow rate 1 ml / min Further, the liquid ethylene random copolymer of the present invention is GP.
The number average molecular weight ( _n ) determined by C is 3 × 10 ² to
Range of 1 × 10 ⁴ , preferably 5 × 10 ^{2 to} 5 × 10 ^3.
Is in the range. The number average molecular weight was measured by GPC pre-calibrated with standards of known molecular weight (monodisperse poly (ethylene) and squalane).

Further, the liquid ethylene-based random copolymer of the present invention,
The following formula (I) [In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the α-olefin component, and P _OE represents the α-olefin-ethylene chain of the entire dyad chain. The molar fraction of is shown. (However, the content mole fraction of each component in the formula (I) is a value calculated excluding the end component)], and the B value represented by the following formula (II) 1.05 ≦ B ≦ 2 (II ) Is satisfied.

The B value is an index representing the distribution state of each monomer component in the copolymer chain. J. Ray (Macromolou
les, 10 , 773 (1977)), J. C. Randall
(Macromoloules, 15 , 353 (1982), J. Pol.
ymer Seience, Polymer Physce Ed. , 11 , 27
5 (1973)), K.S. Kimura (Polymer, 25 , 44
1 (1984)) and the like, and is calculated by determining P _E , P _O and P _OE defined above.

The larger the B value, the smaller the number of blocky chains, and the more uniform the distribution of ethylene and α-olefin, indicating that the copolymer has a narrow composition distribution.

The liquid ethylene random copolymer of the present invention preferably has the following B value.

When the ethylene content of the copolymer is 50 mol% or less: 1.0 + 0.3 × P _E ≦ B ≦ 1 / (1-P _E ), more preferably the general formula 1.0 + 0.4 × P _E ≦ B ≦ 1 / (1-P _E ), particularly preferably the general formula 1.0 + 0.5 × P _E ≦ B ≦ 1 / (1-P _E ), when the ethylene content of the copolymer is 50 mol% or more: 1.3-0.3 × P _E ≦ B ≦ 1 / P _E , more preferably the general formula 1.4−0.4 × P _E ≦ B ≦ 1 / P _E , particularly preferably the general formula 1.5−0.5 × P _E ≦ B ≦ 1 / P _E , and the composition The distribution B value is about 200 in a 10 mmφ sample tube.
The ¹³ C-NMR spectrum of a sample obtained by uniformly dissolving mg of the copolymer in ml of hexachlorobutadiene was measured at a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, and a spectrum width of 1500.
Hz, filter width 1500 Hz, pulse repetition time 4.2 s
ec, pulse width 7 μsec, measurement was performed under the measurement conditions of 2000 to 5000 times of integration, and from this spectrum, P _E , P
It was calculated by _{obtaining O 2} and P _OE .

Furthermore, ¹³ of the liquid ethylene-based random copolymer of the present invention
In the C-NMR spectrum, αβ and βγ signals based on a methylene chain between two adjacent tertiary carbon atoms in the main chain of the copolymer are not observed.

For example, in the copolymer of ethylene and 1-hexene,
Combine the following: When viewed from the tertiary carbon on the left derived from 1-hexene, the three central methylene units are located at positions α, β and γ from the left, while viewed from the tertiary carbon on the right, α and β from the right. ,
It is in the γ position. Therefore, although there are methylene groups in the above binding units that give the signals of αγ and ββ, αβ
And there is no methylene group giving the βγ signal.

Similarly, 1-hexenes bound head-to-tail by the following bonds: Exists only in methylene groups that give α and α signals, and there is no methylene group that gives α, β and βγ signals.

On the other hand, the following combination Each have a methylene group that provides a βγ signal and an αβ signal.

In the present invention, the liquid ethylene random polymer has an iodine value of 0 to
It is in the range of 85, preferably 0 to 50. When the iodine value of the liquid ethylene-based random copolymer of the present invention is a positive value greater than 0, the carbon / carbon based on the ethylene unit or the α-olefin unit at one end of the copolymer molecule is used. Those having an unsaturated bond or having a carbon-carbon unsaturated bond based on an ethylene unit or the α-olefin unit at one end and the carbon-carbon unsaturated at one end of the copolymer molecule It is a mixture with one having no bond. When the iodine value is 0, the copolymer has no unsaturated bond. When the liquid ethylene random copolymer is used as a lubricating oil, its iodine value is 0 to 0.3, preferably 0 to 0.2, and particularly preferably 0.
Those in the range of to 0.1 are suitable.

As is clear from the above description, the liquid ethylene random copolymer of the present invention has a regular bonding direction of the monomer copolymerizable with ethylene.

The liquid ethylene-based random copolymer of the present invention is usually 130
Viscosity index of ~ 350, flash point above 240 ° C, and 0
The pour point below ℃ is shown.

The liquid ethylene random copolymer of the present invention has a narrow molecular weight distribution and composition distribution and is excellent in various properties required for a lubricating oil, as compared with the copolymer obtained using a titanium catalyst. There is. Compared with the copolymer obtained using vanadium catalyst, the molecular weight distribution and the composition distribution are almost the same or narrower, but the arrangement state of the copolymer component in the molecular chain is different and necessary for the lubricating oil. It is excellent in various properties.

〔Example〕

 Next, the present invention will be specifically described with reference to examples.

Example 1 Preparation of Dicornium Catalyst A 100 ml glass flask thoroughly purged with nitrogen was charged with 30 ml of toluene and 2 mmol of bis (cyclopentadienyl) zirconium monochloride monohydride to form a slurry. 20 mmol of trimethylaluminum (1M solution) diluted with toluene was added dropwise thereto at room temperature. After completion of dropping, the temperature was raised to 60 ° C. and the reaction was carried out for 1 hour.
Bis (cyclopentadienyl) zirconium monochloride monohydride was dissolved in toluene and the solution became dark red. In addition, the above reaction went on and off with light.

Preparation of Methylaluminoxane In a 400 ml glass flask thoroughly purged with argon, 13.9 g of magnesium chloride hexahydrate and 125 of toluene.
After charging ml, the mixture was cooled to 0 ° C., and 250 mmol of trimethylaluminum diluted with 125 ml of toluene was added dropwise.
After the dropping was completed, the temperature was raised to 70 ° C. and the reaction was performed at that temperature for 96 hours. After the reaction, solid-liquid separation was performed by filtration, and toluene was removed from the separated liquid under reduced pressure to obtain 7.3 g of white solid methylaluminoxane. The molecular weight determined by freezing point depression in benzene was 1910, and the m value of the aluminoxane was 31. During the polymerization, the aluminoxane was redissolved in toluene before use.

Using a continuous polymerization reactor of polymerization 2,
hr, methylaluminoxane was continuously supplied at a rate of 5 mg atom / hr in terms of aluminum atom, and the zirconium catalyst purified as described above was continuously supplied at a rate of 8 × 10 ^-2 mg atom / hr in terms of zirconium atom, in a polymerization vessel. At the same time ethylene 45 / hr, propylene 240 / h
Polymerization was carried out under the conditions of a polymerization temperature of 40 ° C., a normal pressure, a residence time of 1 hour, and a polymer concentration of 65 g /. The produced polymer solution was continuously withdrawn from the polymerization vessel, and a small amount of methanol was added to terminate the polymerization. The operation of adding a large amount of water to the polymer solution and washing with water was repeated 4 times. Thereafter, toluene was removed from the polymer solution to obtain a colorless transparent liquid polymer. Further, this liquid polymer was dried under reduced pressure (150 mmHg) at 130 ° C. for 12 hours. This liquid polymer has an ethylene content of 50 mol% and a number average molecular weight of n90.
0, w / n 1.71, B value 1.30, kinematic viscosity at 100 ° C 2
The viscosity was 8.1 cst, the viscosity index was 172, the flash point was 261 ° C., and the iodine value was 28. No signals based on αβ and βγ were observed in the ¹³ C-NMR spectrum of the obtained polymer. The activity per unit zirconium was 810 g-polymer / milligram atom-Zr.

Examples 2 to 10 and Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out except that the polymerization was carried out under the conditions shown in Table 1. The ¹³ C-NM of the obtained polymer
In the R spectrum, as in Example 1, signals based on αβ and βγ were not observed. The results are shown in Table 2.

Comparative Example 3 Using the same continuous polymerization apparatus used in Example 1, purified hexane was 2 / hr, ethylaluminum cesecilolide was 48 mg atom / hr in terms of aluminum atom, and vanadyl trichloride was 8 mmol in terms of vanadium atom. It is continuously supplied at a rate of atom / hr, and ethylene 30 / hr, propylene 30 / hr, hydrogen 100 / at the same time in the polymerization vessel.
Polymerization was carried out under the conditions of a polymerization temperature of 35 ° C., a normal pressure, a residence time of 0.5 hours, and a polymer concentration of 49 g /, while being continuously supplied at a rate of hr. The subsequent operation was performed in the same manner as in Example 1. In the ¹³ C-NMR spectrum of the obtained liquid polymer, signals based on αβ and βγ were observed.

Application example 12 Cyclohexane 1 in a stainless steel autoclave
100 g of the liquid polymer obtained in Example 1 and 4 g of a nickel catalyst (N-103 manufactured by Nikko Kagaku Co., Ltd.) were charged, and hydrogenation reaction was carried out at a hydrogen pressure of 25 kg / cm ² gauge and 150 ° C. for 3 hours. After the reaction, further remove cyclohexane,
It was dried under reduced pressure (150 mmHg) at 30 ° C. for 12 hours.
The resulting liquid polymer has a kinematic viscosity at 100 ° C of 28.8cs.
t, viscosity index 171, flash point 264 ° C, pour point -37.5
° C., Four-Ball Test 7.5 kg / cm ^2, was iodine value 0.1.

Application Example 2-8 Application Example 1 of the liquid polymer obtained in Examples 2 to 7 and 10
The hydrogenation reaction was performed in the same manner as in. The results are shown in Table 3.

[Effects of the Invention] The liquid ethylene random copolymer of the present invention has narrow molecular weight distribution and composition distribution. A product obtained by hydrogenating the copolymer has a high viscosity index and a high flash point, a low pour point, excellent shear stability, oxidation stability and thermal stability, and also has excellent oil film strength. Therefore, it is used as a synthetic lubricating oil, and since the liquid ethylene random copolymer of the present invention has a double bond at the molecular end that can react with maleic anhydride, etc., it can be easily modified according to various purposes. Is.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for producing the copolymer of the present invention.

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Claims (2)

[Claims] 1. Ethylene and α-containing 3 to 10 carbon atoms.
A liquid ethylene-based random copolymer from olefin, wherein the content of (a) ethylene component is in the range of 10-85 mol% and the content of α-olefin component is 15-90.
(B) gel permeation chromatography (GP)
The number average molecular weight (n) measured in C) is 3 × 10 ² to 1
× a ^10-4 range, (c) GPC in determined molecular weight distribution (w / n) of 2.5
And (d) the following formula (I) In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the α olephine component,
P _OE represents the molar fraction of all dyad-chain α-olefin / ethylene chains], and the B value is in the range satisfying the following formula (II) 1.05 ≦ B ≦ 2 (II), (e) ^{In the 13} C-NMR spectrum, the αβ and βγ signals based on the methylene chain between two adjacent tertiary carbon atoms in the main chain of the copolymer are not observed, and (f) the iodine value is 0 to 85. The liquid ethylene random copolymer is characterized in that 2. The content of (a) ethylene component is 10 to 85.
Mol% and the content of the α-olefin component having 3 to 10 carbon atoms in the range of 15 to 90 mol%, (b) gel permeation chromatography (GP)
The number average molecular weight (n) measured in C) is 3 × 10 ² to 1
× a ^10-4 range, (c) GPC in determined molecular weight distribution (w / n) of 2.5
And (d) the following formula (I) In the formula, P _E represents the content mole fraction of the ethylene component in the copolymer, P _O represents the content mole fraction of the α-olefin component,
P _OE represents the molar fraction of all dyad-chain α-olefin / ethylene chains], and the B value is in the range satisfying the following formula (II) 1.05 ≦ B ≦ 2 (II), (e) ^{In the 13} C-NMR spectrum, the αβ and βγ signals based on the methylene chain between two adjacent tertiary carbon atoms in the main chain of the copolymer are not observed, and (f) the iodine value is 0 to 85. A synthetic lubricating oil comprising a liquid ethylene-based random copolymer of ethylene and α-olefin having 3 to 10 carbon atoms in the range.