JPH06157644A - Terminal-modified polyolefin - Google Patents

Abstract

PURPOSE:To obtain a nearly monodisperse terminal-modified polyolefin by modifying polypropylene or an ethylene/propylene random copolymer only at the terminals thereof with specific pyridinum derivative units. CONSTITUTION:This polyolefin is obtained by modifying polypropylene or an ethylene/propylene random copolymer only at the terminals thereof with pyridinum derivative units represented by the formula (wherein R is an alkyl or aryl; X is a halide or sulfate ion; and (n) is a number of 1-500). The modification is conducted by reacting vinylpyridine with a living polypropylene or a living ethylene/propylene random copolymer each obtained using a specific polymerization catalyst which causes neither a chain transfer reaction nor a cessation reaction, and quaternizing the resulting polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyolefin having a polymer terminal modified with a pyridinium group unit.

[0002]

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

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyolefin in which only terminals of polypropylene or ethylene-propylene random copolymer are modified with a pyridinium group unit and which is nearly monodisperse.

[0004]

As a result of earnest studies, the inventors of the present invention have found that a living polypropylene or ethylene-propylene random copolymer obtained by using a specific polymerization catalyst without chain transfer reaction or termination reaction. The present invention has been completed by finding that the object of the present invention can be achieved by reacting vinyl pyridine with vinyl pyridine and then quaternizing.

[0005] SUMMARY OF THE INVENTION Namely, the present invention is polypropylene or an ethylene - propylene random copolymer end terminal modified polyolefin comprising modified with pyridinium group unit represented by the following general formula I, general formula I

[0006]

[Chemical 2] [Wherein R represents an alkyl group or an aryl group, and X
Represents halogen or sulfate ion, and n is 1 to 500
Represents the number of. ] Is the gist.

The terminal-modified polyolefin of the present invention has the following general formula II and general formula II

[0008]

[Chemical 3] [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 composed of a vanadium compound and an organoaluminum compound represented by, living polypropylene obtained by polymerizing propylene or a living ethylene-propylene random copolymer obtained by randomly copolymerizing ethylene and propylene, By reacting with vinyl pyridine, a terminal modified polyolefin having a vinyl pyridine unit at the end is synthesized,
It is obtained by quaternizing this polymer with a quaternizing agent such as benzyl bromide in a solvent to obtain a terminal-modified polyolefin having a pyridinium group at the terminal of the polyolefin.

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

[0010]

[Chemical 4][However, R¹~ R³Has the same meaning as above. ] Is represented.
A specific example included in the above formula will be described below.・ R²Is a hydrogen atom, and R¹And R³Is a hydrocarbon group
If R¹/ R³: CH₃/ CH₃, CH₃/ C₂H_Five, C₂
H_Five/ C₂H_Five, CH ₃/ C₆H_Five, C₂H_Five/ C₆H
_Five, C₆H_Five/ C₆H_Five, CH₃/ C₆H_FiveCH₂, C
₆H_FiveCH₂/ C₆H_FiveCH₂, C₂H_Five/ C₆H_FiveC
H₂, C₆H_Five/ C₆H_FiveCH₂．・ R²Is a hydrocarbon group, R¹, R³One of them is water
When the other is a hydrocarbon group in an elementary atom. R²/ R¹Or R³: CH₃/ CH₃, C₂H_Five/ CH
₃, CH₃/ C₂H_Five, C₂H_Five/ C₂H_Five, C₆H_Five
/ CH₃, CH₃/ C₆H_Five, C₆H_Five/ C₂H_Five, C
₂H_Five/ C₆H_Five, C₆H_Five/ C₆H_Five, C₆H_FiveCH
₂/ CH₃, CH₃/ C₆H_FiveCH₂, C₆H_FiveCH₂
/ C₆H_FiveCH₂, C₆H_FiveCH₂/ C ₂H_Five, C₂H
_Five/ C₆H_FiveCH₂, C₆H_FiveCH₂/ C₆H_Five, C₆
H_Five/ C ₆H_FiveCH₂．・ R²Is a hydrogen atom, and R¹, R³Is hydrogen
When an atom is another hydrocarbon group. R¹Or R³: CH₃, C₂H_Five, C₆H_Five, C₆H_Five
CH₂ Among these, the following compounds are particularly desirable.
Good

[0011]

[Chemical 5]

[0012]

[Chemical 6]

[0013]

[Chemical 7]

(B) Organoaluminum compound The organoaluminum compound has the general formula _R'n Al
X'3 _-n (wherein R'is an alkyl group or an aryl group,
X ′ represents a halogen atom or a hydrogen atom, and n is 1 ≦ n <
It is an arbitrary number in the range of 3. ),
Particularly preferred are alkylaluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as dialkylaluminum monohalides, monoalkylaluminum dihalides, and alkylaluminum sesquihalides, or mixtures or complex compounds thereof. Specifically, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, dialkyl aluminum monohalide such as diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, Examples thereof include monoalkyl aluminum dihalides such as ethyl aluminum diiodide and isobutyl aluminum dichloride, and alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride.

The proportion of the vanadium compound and the organoaluminum compound used is 1 to 1,000 moles of the organoaluminum compound per mole of the vanadium compound.

Living Polymerization of Propylene Living polymerization of propylene includes, in addition to homopolymerization of propylene, a small amount of ethylene or 1-butene, 1
It is also possible to polymerize in the presence of an α-olefin such as -hexene or 4-methyl-1-pentene.

The polymerization reaction is inert to the polymerization reaction,
And it is desirable to carry out in a liquid solvent at the time of polymerization, as the solvent, saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane, saturated alicyclic hydrocarbons such as cyclopropane and cyclohexane, benzene. , And aromatic hydrocarbons such as toluene and xylene.

The amount of the polymerization catalyst used during the polymerization of propylene is 1 × 10 ^{−4 to} 0.1 mol of vanadium compound per 1 mol of propylene or a small amount of comonomer.
5 × 10 ^{−4 to} 5 × 10 ⁻² moles, organoaluminum compound 1 × 10 ^{−4 to} 0.5 moles, preferably 1 ×
It is 10 ^{−3 to} 0.1 mol. In addition, vanadium compound 1
The organoaluminum compound is preferably 4 to 4 moles.
100 mol is used.

Living polymerization is usually from -100 ° C to +10.
It is carried out at 0 ° C for 0.5 to 50 hours. The molecular weight and yield of the obtained living polypropylene can be adjusted by changing the reaction temperature and the 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)
Can be a living polymer having a ratio of 1.05 to 1.40.

A reaction accelerator may be used during the polymerization reaction. As the reaction accelerator, anisole, water, oxygen,
Examples thereof 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 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 being nearly monodisperse can be produced.

Living random ethylene-propylene
The copolymerization polymerization reaction is preferably carried out in a solvent which is inert to the polymerization reaction and which is liquid at the time of the polymerization, and examples of the solvent include saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane. Saturated cycloaliphatic 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 contacting the organoaluminum A method of adding ethylene and propylene to a solvent solution containing a compound and a vanadium compound and bringing them into contact with each other.

The amount of the polymerization catalyst used is such that the vanadium compound is 1 × 10 ^{−4 to} 0.
1 mol, preferably 5 × 10 ⁻⁴ mol to 5 × 10 ⁻² mol,
The organoaluminum compound is 1 × 10 ^{−4 to} 0.5 mol, and preferably 1 × 10 ^{−3 to} 0.1 mol. The organoaluminum compound is preferably used in an amount of 4 to 100 mol per mol of the vanadium compound. The molecular weight and yield of the resulting living copolymer can be adjusted by changing the reaction temperature and the reaction time. The present invention has a low polymerization temperature,
In particular, by setting the temperature to -30 ° C or lower, a polymer having a molecular weight distribution close to monodispersion can be obtained, and at -50 ° C or lower, Mw (weight average molecular weight) / Mn (number average molecular weight)
A living ethylene-propylene random copolymer having a ratio of 1.05 to 1.40 is obtained.

A reaction accelerator can be used during the polymerization reaction. As the reaction accelerator, anisole, water, oxygen,
Examples thereof 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 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 use ratio of ethylene and propylene during living polymerization, but if the use ratio of ethylene is increased, the molecular weight distribution of the copolymer becomes wider, which is not desirable. When producing a living copolymer having a high ethylene content and a narrow molecular weight distribution, that is, a monodisperse living copolymer, a small amount of propylene is supplied to the polymerization system before the living copolymerization of ethylene and propylene. By holding for 1 hour, a large amount of ethylene can be introduced into the copolymer while the living copolymer has a narrow molecular weight distribution. As described above, a living ethylene-propylene random copolymer having a number average molecular weight of about 500 to 500,000 (converted to propylene, the same applies hereinafter) and being nearly 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. It is desirable to use the method. The reaction is -100 ℃ to + 150 ℃
At a temperature of 5 minutes to 50 hours. By increasing the reaction temperature or lengthening 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 per mol of living polyolefin.

The reaction product of living polypropylene or ethylene-propylene random copolymer and vinyl pyridine is then contacted with a proton donor to give
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.
The alcohol and the mineral acid may be used at the same time. 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 follows the number average molecular weight (Mn) of about 500 to about 500,000 and the living polypropylene or ethylene-propylene random copolymer itself. Very narrow molecular weight distribution (Mw / Mn = 1.05-1.
40), each of which has 1 to 200 ends,
Desirably it is modified with 1 to 100 vinyl pyridine units. Further, the terminal-modified polyolefin of the present invention is characterized in that the syndiotactic dyad fraction is 0.6 or more.

Quaternization reaction of pyridine ring The polymer obtained as described above is treated with hydrocarbons such as n-heptane, benzene and toluene, n-butyl ether,
After dissolving in a solvent such as ethers such as THF and ketones such as methyl ethyl ketone, add a quaternizing agent such as methyl iodide, methyl bromide, propyl bromide, butyl bromide, benzyl chloride and benzyl bromide. And react at a temperature of 0 to 150 ° C. After completion of the reaction, the reaction solution is poured into methanol to precipitate the polymer.

[0028]

EXAMPLES The present invention will be described below with reference to examples. The characterization of the polymer was carried out 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. Column is Tohso GMH6HT (trade name)
It was used. In the measurement, a standard curve of polystyrene was obtained using a monodisperse polystyrene standard sample manufactured by Tosoh Corporation, and a standard curve of polypropylene was prepared from this by a universal method. Polymer structure determination ( ¹ H-NMR spectrum): JSX GSX-4
00 (trade name), Fourier transform type NMR spectrometer was used under the conditions of 400 MHz, 30 ° C. and pulse interval of 15 seconds. The sample was prepared by dissolving it in deuterated chloroform. ( ¹³ C-NMR spectrum): VFT XL-200 type (trade name) with PFT pulse Fourier transform device
Using, 50MHz, 120 ℃, pulse width 8.2μs
The measurement was performed under the conditions of π / 3, pulse interval of 4 seconds, and integration number of 5,000. Samples were trichlorobenzene and benzene (2:
It was adjusted by dissolving it in the mixed solvent of 1). (Infrared absorption spectrum): The polymer was cast on a KBr plate and measured using a model IR-810 (trade name) infrared spectrophotometer manufactured by JASCO Corporation.

[0029]Example 1 Synthesis of polypropylene modified with terminal vinylpyridine In a 300 ml flask sufficiently replaced with nitrogen gas, n-
100 ml of heptane was added and cooled to -60 ° C. Same temperature
200 mmol of propylene was added to the mixture in n-heptane.
Liquefied and dissolved. Then 15 mmol of Al (C₂H_Five)
₂Cl in n-heptane and 1.5 mmol V
(2-methyl-1,3-butanedionate) ₃Toluene soluble
The liquid was added, and polymerization was started with stirring. Heavy weight of propylene
The combination was carried out at -60 ° C for 1 hour. Then 4-vinylpyridy
(4-VP) 100 mmol was added at -60 ° C.
Then, the mixture was reacted at the same temperature for 1 hour. After that, 500 ml
The reaction solution was poured into ethanol to precipitate a polymer.
The obtained polymer is redissolved in n-heptane and centrifuged.
A supernatant was obtained by separation. 500 ml of this supernatant
Was poured into methanol to precipitate a polymer again. Got
The polymer was washed with methanol 5 times and then at room temperature.
It was dried under reduced pressure to obtain 0.75 g of a polymer. Polymerization obtained
The body's GPC efflux curve was unimodal. Of this polymer
Mn is 3.3 × 10³And Mw / Mn is 1.16.
And the value was close to monodisperse. Of this polymer¹H-NMR
As a result of analysis, a peak (δ =
0.7-1.7 ppm) other than the following chemical shift values
Is observed at the end of the polypropylene chain
It was found that VP was bound.

[0030]

[Chemical 8]

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

Quaternization reaction of pyridine ring This polymer was dissolved in 50 ml of THF, 50 mmol of benzyl bromide was added, and the reaction was carried out under reflux for 5 hours. After the reaction was completed, this solution was poured into 500 ml of methanol to precipitate a polymer. The obtained polymer was washed with methanol 5 times and dried under reduced pressure at room temperature to 0.7.
7 g of polymer was obtained. When IR measurement of the obtained polymer was performed, absorption due to a pyridinium group was observed at 1640 cm ⁻¹ . In addition, 1600 due to pyridine
No absorption of cm ^-1 was observed. From this result, it was confirmed that the pyridine at the polypropylene end was quaternized.

Example 2 Synthesis of Terminal Vinyl Pyridine Modified Polypropylene 100 ml of toluene was placed in a 300 ml flask sufficiently replaced with nitrogen gas and cooled to -78 ° C. 200 mmol of propylene was added at the same temperature and liquefied and dissolved in toluene. Then, a solution of 15 mmol of Al (C ₂ H ₅ ) ₂ Cl in n-heptane and a solution of 1.5 mmol of V (acetylacetonato) _{3 in} toluene were added, and polymerization was started with stirring. Polymerization of propylene was carried out at -78 ° C for 6 hours. Then, except that the reaction condition was -60 ° C. for 2 hours,
Reaction with 4-VP was carried out in the same manner as in Example 1, and Mn =
11.5 × 10 ³ , Mw / Mn = 1.17, vinylpyridine unit number n = 1, end-modified polypropylene 1.6
9 g was obtained. Quaternization reaction of pyridine ring This polymer was reacted with benzyl bromide in the same manner as in Example 1. By IR measurement of the obtained polymer, it was confirmed that the pyridine at the polypropylene terminal was quaternized.

Example 3 An end-modified polypropylene was obtained in the same manner as in Example 1 except that methyl iodide was used in place of benzyl bromide in the quaternization reaction of Example 1. Was subjected to IR measurement of the obtained polymer, the absorption of absorption due to the pyridinium group 1640 cm ^-1 is due to pyridine observed 1600 cm ^-1 had disappeared. From this result, it was confirmed that the propylene-terminated pyridine was quaternized.

Example 4 Synthesis of EPR Modified with Terminal Vinyl Pyridine 500 ml of toluene was placed in a 1.0 liter autoclave sufficiently replaced with nitrogen gas, cooled to -60 ° C., and then 25 mmol of Al (C ₂ H) was added at the same temperature. ₅ ) A solution of ₂ Cl in n-heptane and a solution of 1.5 mmol of V (2-methyl-1,3-butanedionate) _{3 in} toluene were added. Then, after reducing the pressure in the system to 680 mmHg, a mixed gas of ethylene and propylene (40/60 molar ratio) was continuously supplied, and random copolymerization of ethylene-propylene was carried out at -60 ° C for 4 hours. Then, at the same temperature, 4-
After adding 500 mmol of VP at −60 ° C., the temperature of the reaction system was raised to 0 ° C. over 1 hour and reacted at the same temperature for 5 hours. Thereafter, the same treatment as in Example 1 is performed and Mn = 2
End-modified ethylene-propylene random copolymer (EPR) 8.42 g having 8.4 × 10 ³ , Mw / Mn = 1.25, and vinylpyridine unit number n = 10 was obtained. ¹³ C-NMR measurement of the obtained copolymer was performed, and the content of propylene was determined from the areas of the peaks (S) belonging to secondary carbon and the peaks (T) belonging to tertiary carbon based on the following formula. I calculated. As a result, the propylene content in the copolymer was 5
It was 3.9 mol%. Propylene content (mol%) = {T / 1/2 (S + T)}
× 100 In addition, as a result of thermal analysis of this copolymer by a differential scanning calorimeter (DSC), a glass transition temperature (about -10 ° C) due to a propylene homopolymer was not observed. Quaternization reaction of pyridine ring This polymer was reacted with benzyl bromide in the same manner as in Example 1. By IR measurement of the obtained polymer, it was confirmed that the pyridine at the polypropylene terminal was quaternized.

[0036]

[Table 1]

[0037]

INDUSTRIAL APPLICABILITY The polymer of the present invention is used as a compatibilizer for heterogeneous polymers, a polymer modifier for imparting dyeability or adhesiveness to polymers, a viscosity index improver for lubricating oils, microbial trapping agents, etc. be able to.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Ueki 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute

Claims (1)

[Claims] 1. A terminal-modified polyolefin obtained by modifying the terminal of polypropylene or an ethylene-propylene random copolymer with a pyridinium group unit represented by the following general formula I. General formula I [Wherein R represents an alkyl group or an aryl group, and X
Represents halogen or sulfate ion, and n is 1 to 500
Represents the number of. ]