JP3322703B2 - Terminally modified polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a terminal-modified polyolefin.
More specifically, the present invention relates to a terminal-modified polyolefin having a polymer terminal modified with a vinylpyridine unit, and a method for producing the same .

[0002]

2. Description of the Related Art In the conventional polymerization of α-olefins such as propylene with a Ziegler-Natta type catalyst, a chain transfer reaction or a termination reaction occurs, so that it is difficult to modify only the terminal of the obtained polymer with a substituent or the like. It is.

[0003]

SUMMARY OF THE INVENTION The present invention provides a terminal-modified polyolefin in which only the terminal of a polypropylene or an ethylene-propylene random copolymer is modified with a vinylpyridine unit and which is close to monodisperse, and a process for producing the same. With the goal.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that living polypropylene or ethylene-propylene random copolymer obtained using a specific polymerization catalyst which does not involve a chain transfer reaction or a termination reaction. The present inventors have found that the object of the present invention can be achieved by reacting the compound with vinylpyridine.

[0005]Summary of the Invention  That is, the present inventionAccording to the first aspect of the invention,Polypropylene
Of ethylene or ethylene-propylene random copolymerPieceEnd
But, By addition reactionVinylpyr represented by the following general formula I
Gin unit,Number average molecular weight is 500
~ 500,000Terminally modified polyolefin, general formula I

[0006]

Embedded image [Here, n represents the number of 1 to 500] are provided.

[0007] According to the second aspect of the present invention, the first
In the invention of the following, the following general formula II, general formula II,

[0008]

Embedded image [ Wherein , R ^{1 to} R ³ represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. However, at least one of R ^{1 to} R ³ must be a hydrogen atom, but all of R ^{1 to} R ³ must not be hydrogen atoms. In the presence of a catalyst comprising a vanadium compound and an organoaluminum compound represented by
Provided is a method for producing a terminal-modified polyolefin , comprising reacting living polypropylene obtained by polymerizing propylene or a living ethylene-propylene random copolymer obtained by random copolymerizing ethylene and propylene with vinylpyridine. Is done .

Catalyst (a) Vanadium compound The vanadium compound used in the present invention has a general formula II:

[0010]

Embedded image[However, R¹~ R^ThreeIs as defined above. ].
Specific examples included in the above equation will be described below.・ R^TwoIs a hydrogen atom, and R¹And R^ThreeIs a hydrocarbon group
If R¹/ R^Three: CH_Three/ CH_Three, CH_Three/ C_TwoH_Five, C_Two
H_Five/ C_TwoH_Five, CH _Three/ C₆H_Five, C_TwoH_Five/ C₆H
_Five, C₆H_Five/ C₆H_Five, CH_Three/ C₆H_FiveCH_Two, C
₆H_FiveCH_Two/ C₆H_FiveCH_Two, C_TwoH_Five/ C₆H_FiveC
H_Two, C₆H_Five/ C₆H_FiveCH_Two.・ R^TwoIs a hydrocarbon group, and R¹, R^ThreeOne of which is water
When the other element is a hydrocarbon group. R^Two/ R¹Or R^Three: CH_Three/ CH_Three, C_TwoH_Five/ CH
_Three, CH_Three/ C_TwoH_Five, C_TwoH_Five/ C_TwoH_Five, C₆H_Five
/ CH_Three, CH_Three/ C₆H_Five, C₆H_Five/ C_TwoH_Five, C
_TwoH_Five/ C₆H_Five, C₆H_Five/ C₆H_Five, C₆H_FiveCH
_Two/ CH_Three, CH_Three/ C₆H_FiveCH_Two, C₆H_FiveCH_Two
/ C₆H_FiveCH_Two, C₆H_FiveCH_Two/ C _TwoH_Five, C_TwoH
_Five/ C₆H_FiveCH_Two, C₆H_FiveCH_Two/ C₆H_Five, C₆
H_Five/ C ₆H_FiveCH_Two.・ R^TwoIs a hydrogen atom, and R¹, R^ThreeAny of which is hydrogen
When the other atom is a hydrocarbon group. R¹Or R^Three: CH_Three, C_TwoH_Five, C₆H_Five, C₆H_Five
CH_Two Among them, the following compounds are particularly desirable.
New

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

(B) Organoaluminum Compound The organoaluminum compound is represented by the general formula R ' _n Al
X ' _3-n (where R' is an alkyl group or an aryl group,
X ′ represents a halogen atom or a hydrogen atom, and n represents 1 ≦ n <
Any number in the range of 3. ),
For example, an alkylaluminum compound having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as dialkylaluminum monohalide, monoalkylaluminum dihalide, and alkylaluminum sesquihalide, or a mixture or complex compound thereof is particularly preferred. Specifically, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, dialkylaluminum monohalide such as diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, Examples thereof include monoalkylaluminum dihalides such as ethylaluminum diiodide and isobutylaluminum dichloride, and alkylaluminum sesquihalides such as ethylaluminum sesquichloride.

The ratio of the vanadium compound to the organoaluminum compound is from 1 to 1,000 mol per mol of the vanadium compound.

Living Polymerization of Propylene In propylene living polymerization, a small amount of ethylene or 1-butene,
It is also possible to carry out polymerization in the presence of α-olefins such as -hexene and 4-methyl-1-pentene.

The polymerization reaction is inert to the polymerization reaction,
The polymerization is preferably carried out in a solvent which is liquid at the time of polymerization. Examples of the solvent include saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane; cycloaliphatic hydrocarbons such as cyclopropane and cyclohexane; and benzene. And aromatic hydrocarbons such as toluene and xylene.

The amount of the polymerization catalyst used in the polymerization of propylene is 1 × 10 ^{−4 to} 0.1 mol of the vanadium compound per 1 mol of propylene or propylene and a small amount of comonomer.
Desirably, 5 × 10 ^{−4 to} 5 × 10 ⁻² mol, and the organoaluminum compound is 1 × 10 ^{−4 to} 0.5 mol, desirably 1 ×.
It is 10 ^{-3 to} 0.1 mol. In addition, vanadium compound 1
Per mole, the organoaluminum compound is desirably from 4 to
100 moles are used.

Living polymerization is usually carried out at a temperature between -100 ° C and + 10 ° C.
Performed at 0 ° C. for 0.5-50 hours. The molecular weight and yield of the obtained living polypropylene can be adjusted by changing the reaction temperature and reaction time. By setting the polymerization temperature to a low temperature, particularly -30 ° C or lower, a polymer having a molecular weight distribution close to monodispersion can be obtained. At −50 ° C. or lower, Mw (weight average molecular weight) / Mn (number average molecular weight)
Is 1.05 to 1.40.

At the time of the polymerization reaction, a reaction accelerator can be used. Reaction accelerators include anisole, water, oxygen,
Examples include alcohols (methanol, ethanol, isopropanol, etc.) and esters (ethyl benzoate, ethyl acetate, etc.). The amount of the accelerator used is usually 0.1 to 2 mol per 1 mol of the vanadium compound. By the above method, living polypropylene having a number average molecular weight of about 500 to about 500,000 and nearly monodisperse can be produced.

Living random of ethylene-propylene
The copolymerization reaction is desirably performed in a solvent that is inert to the polymerization reaction and is liquid at the time of the polymerization. Examples of the solvent include saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane, and heptane. And saturated alicyclic hydrocarbons such as cyclopropane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. The method of contacting ethylene and propylene with the polymerization catalyst can be arbitrarily selected, but is preferably a method of sequentially adding a solution of an organoaluminum compound and a solution of a vanadium compound to a solvent solution of ethylene and propylene, or For example, a method in which ethylene and propylene are added to a solvent solution containing a compound and a vanadium compound and brought into contact with each other is used.

The amount of the polymerization catalyst used is from 1 × 10 ^{-4 to} 0.1% of the vanadium compound per mole of ethylene and propylene.
1 mol, preferably 5 × 10 ⁻⁴ mol to 5 × 10 ⁻² mol,
The amount of the organic aluminum compound is 1 × 10 ^{−4 to} 0.5 mol, preferably 1 × 10 ^{−3 to} 0.1 mol. The organoaluminum compound is preferably used in an amount of 4 to 100 mol per 1 mol of the vanadium compound. The molecular weight and the yield of the obtained living copolymer can be adjusted by changing the reaction temperature and the reaction time. The present invention, the polymerization temperature is low,
In particular, by setting the temperature to -30 ° C or lower, a polymer having a molecular weight distribution close to monodispersion can be obtained.
Of 1.05 to 1.40 to obtain a living ethylene-propylene random copolymer.

At the time of the polymerization reaction, a reaction accelerator can be used. Reaction accelerators include anisole, water, oxygen,
Examples include alcohols (methanol, ethanol, isopropanol, etc.) and esters (ethyl benzoate, ethyl acetate, etc.). The amount of the accelerator used is usually 0.1 to 2 mol per 1 mol of the vanadium compound. The proportion of ethylene and propylene in the living copolymer is usually up to 90 mol% ethylene. This can be adjusted by changing the usage ratio of ethylene and propylene during living polymerization. However, if the usage ratio of ethylene is increased, the molecular weight distribution of the copolymer becomes undesirably wide. When the ethylene content is high and the molecular weight distribution is narrow, that is, when producing a living copolymer close to monodispersion, a small amount of propylene is supplied to the polymerization system before living copolymerizing ethylene and propylene, and 0.1 By holding for 1 hour, it is possible to introduce a large amount of ethylene into the copolymer while keeping the molecular weight distribution of the living copolymer narrow. As described above, a living ethylene-propylene random copolymer having a number average molecular weight of about 500 to 500,000 (in terms of propylene, the same applies hereinafter) and almost monodisperse can be produced.

Reaction with vinyl pyridine The reaction between living polypropylene or ethylene-propylene random copolymer and vinyl pyridine is carried out by supplying vinyl pyridine to a reaction system in which living polypropylene or ethylene-propylene random copolymer is present. The preferred method is Reaction is -100 ° C to + 150 ° C
For 5 minutes to 50 hours. By increasing the reaction temperature or increasing the reaction time, the modification rate of the polyolefin terminal with the vinylpyridine unit can be increased. Vinyl pyridine is used in an amount of 1 to 1,000 mol based on 1 mol of living polyolefin.

The reaction product of living polypropylene or ethylene-propylene random copolymer with vinylpyridine is then contacted with a proton donor,
The end-modified polyolefin of the present invention is obtained. Examples of the proton donor include alcohols such as methanol, ethanol and phenol, and mineral acids such as hydrochloric acid and sulfuric acid.
Alcohols and mineral acids may be used simultaneously. The proton donor is usually used in large excess. The contact with the proton donor is usually performed at -100 ° C to + 100 ° C for 1 minute to 10 hours.

The polyolefin of the present invention obtained as described above has a number average molecular weight (Mn) of about 500 to about 500,000, and follows the living polypropylene or the ethylene-propylene random copolymer itself. Very narrow molecular weight distribution (Mw / Mn = 1.05-
1.40), and the terminal is 1 to 200
, Preferably 1 to 100 vinylpyridine units. One feature of the terminal-modified polyolefin of the present invention is that the syndiotactic dyad fraction is 0.6 or more.

[0027]

The present invention will be described below with reference to examples. In addition, the characterization of the polymer was performed by the following method. -Molecular weight and molecular weight distribution GPC (gel permeation chromatography) model 150 manufactured by Waters was used. Solvent: o-dichlorobenzene, measurement temperature: 135 ° C, solvent flow rate: 1.0
ml / min. The column is GMH6HT (trade name) manufactured by Tosoh Corporation
It was used. In the measurement, a calibration curve of polystyrene was obtained using a standard monodisperse polystyrene sample manufactured by Tosoh Corporation, and a calibration curve of polypropylene was prepared from the calibration curve by the universal method. · Structure Determination ⁽¹ H-NMR spectrum) of the polymer: manufactured by JEOL Ltd. GSX-4
00 (trade name), measured using a Fourier transform MMR spectrometer under the conditions of 400 MHz, 30 ° C., and pulse interval of 15 seconds. The sample was prepared by dissolving in deuterated chloroform. ( ^13C -NMR spectrum): Using a Varian model XL-200 (trade name) with a PFT pulse Fourier transform device, 50 MHz, 120 ° C., pulse width 8.2 μm.
The measurement was performed under the following conditions: sπ / 3, pulse interval: 4 seconds, and number of integration: 5,000. The sample was prepared by dissolving in a mixed solvent of trichlorobenzene and benzene (2: 1).

Example 1 A 300 ml flask sufficiently purged with nitrogen gas was charged with n-
100 ml of heptane was charged and cooled to -60C. At the same temperature, 200 mmol of propylene was added and liquefied and dissolved in n-heptane. Then, 15 mmol of Al (C ₂ H
_{5) 2} Cl in n- heptane solution and 1.5 mmol of V (2-methyl-1,3-butanedionate) ₃ in toluene was added to initiate the polymerization with stirring. The polymerization of propylene was performed at -60 ° C for 1 hour. Next, 100 mmol of 4-vinylpyridine (4-VP) was added at -60 ° C, and the mixture was reacted at the same temperature for 1 hour. Thereafter, the reaction solution was poured into 500 ml of ethanol to precipitate a polymer.
The obtained polymer was dissolved again in n-heptane and centrifuged to obtain a supernatant. 500 ml of this supernatant
And the polymer was precipitated again. The obtained polymer was washed with methanol five times and then dried under reduced pressure at room temperature to obtain 0.75 g of a polymer. The GPC outflow curve of the obtained polymer was monomodal. M of this polymer
n was 3.3 × 10 ³ , and Mw / Mn was 1.16, a value close to monodispersion. As a result of ¹ H-NMR analysis of this polymer, a peak (δ = 0.
7 to 1.7 ppm), a peak consisting of the following chemical shift values was observed, and 4-VP was added to the end of the polypropylene chain.
Was found to be bound.

[0029]

Embedded image

From the area ratio between the proton signal (δ = 0.7 to 1.7 ppm) of the polypropylene part and the proton signal (a) of the 4-VP unit, two 4-VP units are bonded to the end of the polypropylene chain. It was confirmed that.

[0031]Example 2  1.5 liter autoclay sufficiently purged with nitrogen gas
Put 400 ml of n-heptane into the tube and cool to -60 ° C.
Was. At the same temperature, 200 g of propylene was added, and n-heptane was added.
Liquefied and dissolved therein. Then 50 mmol of Al
(C₂H₅)₂Cl in n-heptane and 0.6
Limol of V (2-methyl-1,3-butanedionato)₃
Toluene solution was added and polymerization was started with stirring.
Continued for a while. Then at the same temperature 500 mmol of 4-VP
After the addition, the temperature of the reaction system is increased over 1 hour.0Rise to ℃
And reacted with 4-VP at 0 ° C. for 10 hours. Less than,
The same treatment as in Example 1 was carried out, and the
Lipropylene was obtained.

Example 3 100 ml of toluene was placed in a 300 ml flask sufficiently purged with nitrogen gas, and cooled to -78 ° C. At the same temperature, 200 mmol of propylene was added and liquefied and dissolved in toluene. Then 15 mmoles of _{Al (C 2 H 5) 2} Cl in n- heptane solution and 1.5 mmol of V (acetylacetonato) ₃ in toluene was added to initiate the polymerization with stirring. The polymerization of propylene was performed at -78 ° C for 3 hours. Then, the reaction with 4-VP was carried out in the same manner as in Example 1 except that the reaction conditions were changed to -60 ° C for 2 hours, to obtain a terminal-modified polypropylene having the properties shown in Table 1.

[0033]Example 4  1.0-liter autoclay sufficiently purged with nitrogen gas
500 ml of toluene was put in the tube and cooled to -60 ° C.
Then, at the same temperature, 25 mmol of Al (C₂H₅)₂Cl
n-Heptane solution and 1.5 mmol of V (2-methyl
Ru-1,3-butanedionato)₃Add toluene solution
Was. Next, after the pressure in the system was reduced to 680 mmHg,
A mixed gas of titanium and propylene (40/60 molar ratio)
Continuous supply, random copolymerization of ethylene and propylene
The combination was performed at -60 ° C for 4 hours. Then, at the same temperature 4-
After addition of 500 mmol of VP at −60 ° C.,
Raise the temperature to 0 ° C over 1 hour, and wait 5 hours at the same temperature.
I responded. Hereinafter, processing is performed in the same manner as in Example 1, and shown in Table 1.
Properties of terminally modified ethylene-propylene random copolymer
I got Of the resulting copolymer¹³Perform C-NMR measurement
And peak (S) attributed to secondary carbon and attributed to tertiary carbon
From the area of the peak (T)
Was calculated. As a result, the propylene in the copolymer
The len content was 53.9 mol%. Propylene content (mol%) =[T / {(T + S) / 2}]× 100 The copolymer was measured by a differential scanning calorimeter (DSC).
As a result of thermal analysis, it was found that glass due to propylene homopolymer
No transition temperature (about −10 ° C.) was observed.

Example 5 Same as Example 1 except that 2-vinylpyridine (2-VP) was used instead of 4-vinylpyridine (4-VP) and the reaction conditions were changed to -40 ° C. for 1 hour. Thus, a terminal-modified polypropylene having the properties shown in Table 1 was obtained.

[0035]

[Table 1]

[0036]

The polymer of the present invention can be used as a compatibilizer for different polymers, a polymer modifier for imparting dyeability and adhesion to the polymer, a viscosity index improver for lubricating oil and the like. Further, a compound in which the pyridine ring has been quaternized can be used as a microorganism capturing agent.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Ueki 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. (56) References JP-A-4-178407 (JP, A) JP-A-63-113002 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (2)

(57) [Claims] 1. A number-average molecule in which one end of a polypropylene or an ethylene-propylene random copolymer is modified by a substituent represented by the following general formula I by an addition reaction.
An end-modified polyolefin in an amount of 500 to 500,000 . Formula I [However, n represents a number of 1 to 500] 2. A compound represented by the following general formula II : [Wherein, R ^{1 to} R ³ represent a hydrogen atom or a carbon atom having 1 to 8 carbon atoms.
Shows a hydride group. Provided that at least one of R ^{1 to} R ³ is
It must be a hydrogen atom, but all of R ^{1 to} R ³ are hydrogen
Must not be an atom. ] Vanadium compound represented by
In the presence of a catalyst consisting of a product and an organoaluminum compound,
Living polypropylene obtained by polymerizing propylene
Or obtained by random copolymerization of ethylene and propylene
Living ethylene-propylene random copolymer
Is reacted with vinylpyridine.
Item 2. The method for producing a terminal-modified polyolefin according to Item 1 .