JPH05320225A - Method for producing end-modified polyolefin - Google Patents

Abstract

(57) [Summary] [Object] The present invention provides a method for producing a polyolefin in which only terminals of polypropylene or an ethylene-propylene random copolymer are modified with a (meth) acrylic acid chloride unit and which is nearly monodisperse. The purpose is to [Structure] General Formula I [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 consisting 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 random copolymerization of ethylene and propylene, , The general formula II: [However, R represents a hydrogen atom or a methyl group. ] It reacts with the (meth) acrylic acid chloride represented by these, Then, the manufacturing method of the terminal (meth) acrylic acid chloride modified polyolefin characterized by precipitating a reaction product in an aproton-donating organic solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyolefin having a polymer terminal modified with a (meth) acrylic acid chloride 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]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a polyolefin in which only terminals of polypropylene or an ethylene-propylene random copolymer are modified with a methacrylic acid (acrylic acid) chloride unit and which is nearly monodisperse. The purpose is to do.

[0004]

As a result of intensive studies, the present inventors have found that living polypropylene or ethylene-propylene random copolymer obtained by using a specific polymerization catalyst without chain transfer reaction or termination reaction. The present invention was completed by discovering that the object of the present invention can be achieved by reacting methacrylic acid (acrylic acid) chloride with, and then depositing the reaction product in an aproton-donating organic solvent.

[0005] SUMMARY OF THE INVENTION Namely, the present invention relates to compounds of the general formula I

[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 consisting 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 random copolymerization of ethylene and propylene, , General formula II

[Chemical 4] [However, R represents a hydrogen atom or a methyl group. ] A method for producing a terminal (meth) acrylic acid chloride-modified polyolefin in which a reaction product is precipitated in an aproton-donating organic solvent after being reacted with a (meth) acrylic acid chloride represented by

The end-modified polyolefin obtained by the production method of the present invention is usually obtained in the form of a composition having a terminal represented by the following general formula III. General formula III

[Chemical 5] [However, R has the same meaning as described above, and n is 0.1 to 10
Represents the number of 0]

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

[Chemical 6][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, R³Is either water
When the other is a hydrocarbon group in the 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
CH₂And the like. Among these, the following compounds are particularly
Is desirable.

[Chemical 7]

[Chemical 8]

[Chemical 9]

(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, heptane, saturated alicyclic hydrocarbons such as cyclopropane, 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 the vanadium compound per 1 mol of propylene or a small amount of propylene and a comonomer.
5 × 10 ^{−4 to} 5 × 10 ⁻² mol, preferably 1 × 10 ^{−4 to} 0.5 mol of organoaluminum compound, 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.), esters (ethyl benzoate, ethyl acetate, etc.) and the like. The amount of the promoter used is vanadium compound 1
It is usually 0.1 to 2 mol per mol. By the above method, a 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, aromatic hydrocarbons such as benzene, toluene, and xylene. The method of contacting the polymerization catalyst with ethylene and propylene 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 obtained living copolymer can be adjusted by changing the reaction temperature and the reaction time. The present invention, the polymerization temperature is low,
Particularly, 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 may be used during the polymerization reaction. As the reaction accelerator, anisole, water, oxygen,
Examples thereof include alcohols (methanol, ethanol, isopropanol, etc.), esters (ethyl benzoate, ethyl acetate, etc.) and the like. The amount of the accelerator used is vanadium compound 1
It is usually 0.1 to 2 mol per mol. 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, and 0.1 By holding for 1 hour, a large amount of ethylene can be introduced into the copolymer while the molecular weight distribution of the living copolymer remains narrow. 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.

Methacrylic acid (acrylic acid) chloride
Methacrylic acid (acrylic acid) reacted with living polypropylene or ethylene-propylene random copolymer
Chloride (hereinafter referred to as compound I) has the general formula II,

[Chemical 10] It is represented by. In the formula, R is a hydrogen atom or a methyl group. The reaction between the living polypropylene or the ethylene-propylene random copolymer and the compound I is preferably carried out by supplying the compound I to the reaction system in which the living polypropylene or the ethylene-propylene random copolymer is present and causing the reaction. The reaction is carried out at a temperature of -100 ° C to + 150 ° C for 5 minutes to 50 hours. By increasing the reaction temperature or lengthening the reaction time, the modification rate of the polyolefin terminal with the compound I unit can be increased.
Compound I is based on 1 mol of living polyolefin,
It is used in an amount of 1 to 1,000 mol.

The reaction product of living polypropylene or ethylene-propylene random copolymer and compound I is then precipitated in an aproton donating organic solvent. Examples of the aproton-donating organic solvent used in the present invention include ketones such as acetone and methyl ethyl ketone, esters such as methyl formate and ethyl acetate, and preferably acetone and ethyl acetate. Precipitation of the reaction product in the aproton donating organic solvent is usually -100 ° C to 1
It is carried out at 00 ° C for 1 minute to 10 hours. The non-proton donating organic solvent is usually used in large excess relative to the reaction product.

The polyolefin obtained by the production method of the present invention has a very narrow number average molecular weight (Mn) of about 500 to about 500,000, and the living polypropylene or ethylene-propylene random copolymer itself is very narrow. Molecular weight distribution (Mw / Mn = 1.05 to 1.4
0) and each end is 0.1-100
Preferably 0.2 to 50, more preferably 0.3
˜25 modified with the Compound I unit.
Further, the end-modified polypropylene of the present invention is characterized in that the syndiotactic dyad fraction is 0.6 or more.

[0021]

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 A 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 by the universal method. -Structural determination of polymer ( ¹³ C-NMR spectrum): JSX-4 manufactured by JEOL Ltd.
00 (trade name), Fourier transform type NMR spectrometer, 100 MHz, 30 ° C., pulse width 8.5 μ
The measurement was performed under the conditions of s π / 3, pulse interval of 9 seconds, and number of integration times of 30,000. The sample was prepared by dissolving it in deuterated chloroform. (Infrared absorption spectrum): The polymer was cast on a KBr plate and model IR-810 manufactured by JASCO Corporation
(Brand name) It measured using the infrared spectrophotometer.

[0022]Example 1 A 300 ml flask sufficiently replaced with nitrogen gas was added with 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 (C
₂H_Five)₂Cl in n-heptane and 1.5 mmol
V (2-methyl-1,3-butanedionate) ₃Torue
Solution was added, and the polymerization was started with stirring. propylene
Was polymerized at -60 ° C for 1 hour. Then methacrylic acid
Add 50 mmol of chloride (MACl) at -60 ° C.
Then, the mixture was reacted at the same temperature for 1 hour. After that, 500 ml
Pour the reaction solution into acetone to precipitate the polymer.
It was The precipitate is dissolved again in n-heptane and centrifuged.
A more supernatant liquid was obtained. Add 500 ml of the supernatant to the supernatant.
It was poured into seton and the polymer was precipitated again. The obtained po
The limmer was washed 5 times with acetone and then dried under vacuum at room temperature.
Then, 0.95 g of a polymer was obtained.

The GPC efflux curve of the resulting polymer was unimodal. Mn of this polymer was 3.4 × 10 ³ , and Mw / Mn was 1.18, which was a value close to monodispersion.
Infrared absorption spectrum (IR) analysis of this polymer confirmed absorption at 1790 cm ⁻¹ based on the carbonyl of the acid chloride group. Further, as a result of ¹³ C-NMR analysis, a peak due to carbon of polypropylene (δ = 10 to 50)
In addition to (ppm), peaks having the following chemical shift values were observed.

[Chemical 11] In addition, a peak (δ =
From 10 to 50 ppm) and the area ratio of the peak (a) belonging to the carbon of the MACl unit, it was found that 2.0 MACl units were introduced at the terminal of polypropylene as described below.

[Chemical formula 12] In order to measure the syndiotactic dyad fraction of the obtained polypropylene, living polymerization of propylene was separately carried out by the same operation as above, and then the reaction solution was cooled to −78 ° C.
Polymerization was quickly stopped by pouring into 500 ml of an ethanol-hydrochloric acid solution cooled to 50 ° C.
It was washed 5 times with 1 L of ethanol and dried at room temperature to obtain polypropylene. Next, the resulting polypropylene ¹³ C-N
MR analysis was performed. The stereoregularity of polypropylene calculated from the multiplex intensity ratio of methyl carbon in the spectrum is shown below. Triad fraction Diad fraction ^a) [rr] [rm] [mm] [r] 0.629 0.314 0.057 0.786 a) Calculated from the triad fraction

Example 2 400 ml of n-heptane was placed in a 1.5 liter autoclave sufficiently replaced with nitrogen gas and cooled to -60 ° C. 200 g of propylene was added at the same temperature and liquefied and dissolved in n-heptane. Then 50 mmol Al
A solution of (C ₂ H ₅ ) ₂ Cl in n-heptane and 0.6 mmol of V (2-methyl-1,3-butanedionate) ₃ toluene solution were added, and polymerization of propylene was started with stirring and continued for 10 hours. .. Then, at the same temperature, MAC125
After adding 0 mmol, the temperature of the reaction system was raised to -40 ° C over 1 hour, and the reaction with MAC1 was performed at -40 ° C for 5 hours.
Went on time. Thereafter, the same treatment as in Example 1 was carried out to obtain a terminal-modified polypropylene having the properties shown in Table 1.

Example 3 100 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 15 mmol of Al (C ₂ H ₅ ) ₂ C
1 n-heptane solution and 1.5 mmol V (acetylacetonato) ₃ toluene solution were added, and polymerization was started with stirring. Polymerization of propylene was carried out at -78 ° C for 3 hours. Then, except that the reaction condition was 0 ° C. for 2 hours,
Reaction with MAC1 was performed in the same manner as in Example 1 to obtain a terminal-modified polypropylene having the properties shown in Table 1.

[0026]Example 4 500 ml autoclave fully replaced with nitrogen gas
250 ml of n-heptane, and cooled to -60 ° C.
Then, at the same temperature, 15 mmol of Al (C₂H_Five) ₂Cl
N-heptane solution and 1.5 mmol of V (2-methyl
Le-1,3-butane dionato)₃Add toluene solution
It was Next, after reducing the pressure in the system to 700 mmHg,
Mixed gas of ethylene and propylene (40/60 molar ratio)
Is continuously supplied, and a random mixture of ethylene and propylene
The polymerization was carried out at -60 ° C for 1 hour. Then, at the same temperature, M
Add 100 mmol of ACl and react at the same temperature for 1 hour.
Let Thereafter, the same treatment as in Example 1 was performed, and the properties shown in Table 1 were used.
A terminal modified ethylene-propylene random copolymer of
It was Of the obtained copolymer¹³C-NMR measurement is performed
Peak (S) attributed to carbon and peak attributed to tertiary carbon
Content of propylene based on the area
The amount was calculated. As a result, the propylene content in the copolymer
The amount was 53.4 mol%. Propylene content (mol%) = {T / 1/2 (S + T)}
× 100 In addition, this copolymer was analyzed by a differential scanning calorimeter (DSC).
As a result of thermal analysis, the amount of glass caused by the propylene homopolymer
No transition temperature (about -10 ° C) was observed.

[0027]

[Table 1]

[0028]

INDUSTRIAL APPLICABILITY The polymer of the present invention can be used as a compatibilizing agent for different polymers, a polymer modifier for imparting dyeability or adhesiveness to the polymer, a viscosity index improver for lubricating oil, and the like.

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

Claims (1)

[Claims] 1. The general formula I: [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 consisting 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 random copolymerization of ethylene and propylene, , The general formula II: [However, R represents a hydrogen atom or a methyl group. ] It reacts with the (meth) acrylic acid chloride represented by these, Then, the manufacturing method of the terminal (meth) acrylic acid chloride modified polyolefin characterized by precipitating a reaction product in an aproton-donating organic solvent.