JP3164633B2 - 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 polyolefin having a polymer terminal modified with a (meth) acrylic acid unit.

[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 An object of the present invention is to provide a polyolefin in which only the terminal of a polypropylene or ethylene-propylene random copolymer is modified with methacrylic acid (acrylic acid) units and which is close to monodisperse. And

[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 styrene with methacrylic acid (acrylic acid), thereby completing the present invention.

[0005]Summary of the Invention  That is, the present invention relates to polypropylene or ethylene
The terminal of the propylene random copolymer is represented by the following general formula I.
A terminally modified polyolefin modified with a substituent
General formula I

Embedded image [However, R represents a hydrogen atom or a methyl group. ].

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

Embedded image Wherein R has the same meaning as described above, and m is 0.1 to 10
Represents the number 0)

The terminal-modified polyolefin of the present invention has the following general formula III:

Embedded image [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 the following formula, living polypropylene obtained by polymerizing propylene or a living ethylene-propylene random copolymer obtained by random copolymerizing ethylene and propylene, General formula IV

Embedded image Wherein R is as defined above. Methacrylic acid (acrylic acid) chloride represented by the formula
By reacting an H aqueous solution, a terminal-modified polyolefin having sodium (meth) acrylate at the terminal is synthesized. Further, the terminal of sodium (meth) acrylate is HC
It can be produced by neutralizing with l.

[0008]catalyst  (A) Vanadium compound The vanadium compound used in the present invention has a general formula II
I,

Embedded image [However, R ^{1 to} R ³ are as defined above. ].
Specific examples included in the above equation will be described below. · ^{R 2} is a hydrogen atom, when ^{R 1} and ^{R 3} is a hydrocarbon group. _{^{R 1 / R 3: CH 3}} / CH 3, CH 3 / C 2 H 5, C 2
_{H 5 / C 2 H 5,} CH 3 / C 6 H 5, C 2 H 5 / C 6 H
_{5, C 6 H 5 / C} 6 H 5, CH 3 / C 6 H 5 CH 2, C
_{6 H 5 CH 2 / C 6} H 5 CH 2, C 2 H 5 / C 6 H 5 C
_{H 2, C 6 H 5 /} C 6 H 5 CH 2. · R ² is a hydrocarbon group, when the other either a hydrogen atom of R ^1, R ³ is a hydrocarbon group. R ² / ^{R 1} or _{^{R 3: CH 3 / CH 3}} , C 2 H 5 / CH
_{3, CH 3 / C 2 H} 5, C 2 H 5 / C 2 H 5, C 6 H 5
/ CH ₃ , CH ₃ / C ₆ H ₅ , C ₆ H ₅ / C ₂ H ₅ , C
_{2 H 5 / C 6 H 5} , C 6 H 5 / C 6 H 5, C 6 H 5 CH
₂ / CH ₃ , CH ₃ / C ₆ H ₅ CH ₂ , C ₆ H ₅ CH ₂
/ C ₆ H ₅ CH ₂ , C ₆ H ₅ CH ₂ / C ₂ H ₅ , C ₂ H
_{5 / C 6 H 5 CH 2} , C 6 H 5 CH 2 / C 6 H 5, C 6
_{H 5 / C 6 H 5 CH} 2. -The case where R ² is a hydrogen atom, one of R ¹ and R ³ is a hydrogen atom, and the other is a hydrocarbon group. R ¹ or R ³ : CH ₃ , C ₂ H ₅ , C ₆ H ₅ , C ₆ H ₅
CH _{2 and the} like are mentioned, and among these, the following compounds are particularly desirable.

Embedded image

Embedded image

Embedded image

(B) Organoaluminum compound The organoaluminum compound is represented by the general formula R _n AlX
_3-n (where R represents an alkyl group or an aryl group, X represents a halogen atom or a hydrogen atom, and n is an arbitrary number in the range of 1 ≦ n <3), for example, dialkyl Particularly preferred are alkylaluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as aluminum monohalide, monoalkylaluminum dihalide, and alkylaluminum sesquihalide, or mixtures or complex compounds thereof. 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 use ratio of the vanadium compound to the organoaluminum compound is 1 to 1,000 mol per mol of the vanadium compound.

Living Polymerization of Propylene In the living polymerization of propylene, 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 of -100 ° C to + 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 800 to about 400,000 and close to monodispersion 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.

The amount of the polymerization catalyst used is such that the vanadium compound is contained in an amount of 1 × 10 ^{-4 to} 0.1 / mol 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 at -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)
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), 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.

[0019]With methacrylic acid (acrylic acid) derivatives
Yes  Living polypropylene or ethylene-propylene run
Methacrylic acid (acrylic acid) reacted with dam copolymer
The derivative (hereinafter, referred to as compound I) has the general formula IV:

Embedded image Is represented by In the formula, R is as described above. The reaction between the living polypropylene or the ethylene-propylene random copolymer and the compound I is preferably a method in which the compound I is supplied to a reaction system in which the living polypropylene or the ethylene-propylene random copolymer is present and reacted. The reaction is performed at a temperature of -100 ° C to + 150 ° C for 5 minutes to
Perform for 50 hours. By increasing the reaction temperature or lengthening the reaction time, the modification ratio of the polyolefin terminal with the compound I unit can be increased. Compound I is
1 to 1.00 per mole of living polyolefin
0 mol is used.

The reaction product of the living polypropylene or the ethylene-propylene random copolymer with the compound I is then reacted with a NaOH solution, and then brought into contact with a proton donor to obtain the terminal-modified polyolefin of the present invention. As the proton donor, methanol,
Examples include alcohols such as 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 +1
Performed at 00 ° 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 800 to about 400,000, and follows the living polypropylene or the ethylene-propylene random copolymer itself. Very narrow molecular weight distribution (Mw / Mn = 1.05-1.
40) and their terminals are 0.1 to 100
, Preferably 0.2 to 50, more preferably 0.3
Modified with ~ 25 of the above Compound I units.
One feature of the terminal-modified polyolefin of the present invention is that the syndiotactic dyad fraction is 0.6 or more.

[0022]

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 monodisperse polystyrene standard 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), using a Fourier transform type NMR spectrometer at 400 MHz, 30 ° C., and a pulse interval of 15 seconds. The sample was prepared by dissolving in deuterated chloroform. ( ^13C -NMR spectrum): Model XL-200 (trade name) manufactured by Varian with a PFT pulse Fourier transform device.
, 50MHz, 120 ° C, pulse width 8.2μs
The measurement was performed under the following conditions: π / 3, pulse interval: 4 seconds, and number of integration: 5,000. The samples were trichlorobenzene and benzene (2:
It was adjusted by dissolving 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.

[0023]Example 1 In a 300 ml flask sufficiently purged with nitrogen gas, add n-
100 ml of heptane was charged and cooled to -60 ° C. Same temperature
And 200 mmol of propylene are added, and in n-heptane
Liquefied and dissolved. Then, 15 mmol of Al (C
_TwoH_Five)_TwoCl in n-heptane and 1.5 mmol
V (2-methyl-1,3-butanedionato) _ThreeTorue
The polymerization solution was added, and polymerization was started with stirring. propylene
Was carried out at −60 ° C. for 1 hour. Then methacryl
100 mmol of acid chloride (MACl) at -60 ° C
It was added and reacted at the same temperature for 1 hour. After that, 20wt%
In 500 ml of acetone to which 10 ml of NaOH solution was added
The reaction solution was poured into the mixture to precipitate a polymer. Got
The polymer was dissolved again in n-heptane and centrifuged.
A supernatant was obtained. The supernatant is added to 500 ml
And the polymer was precipitated again. Of this polymer
1570 cm after IR analysis^-1COO^-(Mosquito
Absorption based on (rubonate anion) was observed. Next,
Dissolve the polymer in THF until pH ~ 7
HCl was added and stirred. The solution was added to 500 ml
And polymer was precipitated and washed 5 times with acetone.
After drying at room temperature, 1.10 g of a polymer was obtained.

The GPC runoff curve of the resulting polymer was unimodal. Mn of this polymer was 3.7 × 10 ³ , M
w / Mn was 1.19, a value close to monodispersion. When the infrared absorption spectrum (IR) of this polymer was measured, 1
At 705 cm ^-1 , absorption based on the absorption of the carbonyl group of -COOH was observed. Further, as a result of ¹ H-NMR analysis, a peak (δ = 0.7 to 1.7 p) due to polypropylene was obtained.
pm), peaks consisting of the following chemical shift values were observed.

Embedded image Further, as a result of ¹³ C-NMR analysis, a peak attributable to carbon of the COOH group was observed at 185 ppm. From the above results, it was found that the methacrylic acid unit was bonded to the terminal of the polypropylene. Also, the carbon signal of the polypropylene part and the COO of the methacrylic acid unit
From the area ratio of the carbon signal of the H group, it was confirmed that six methacrylic acid units were bonded to the end of the polypropylene chain.

Example 2 400 ml of n-heptane was placed in a 1.5 liter autoclave sufficiently purged with nitrogen gas, and cooled to -60 ° C. At the same temperature, 200 g of propylene was added and liquefied and dissolved in n-heptane. Then 50 mmol of Al
(C ₂ H ₅₎ the ₂ Cl in n- heptane solution and 0.6 mmol of V (2-methyl-1,3-butanedionate) ₃ in toluene was added, to initiate polymerization of propylene with stirring continued for 15 hours did. Then, at the same temperature, MAC15
After the addition of 00 mmol, the temperature of the reaction system was raised to -40 ° C over 1 hour, and the reaction with MACl was carried out at -40 ° C for 5 hours. 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 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 mmol of Al (C ₂ H ₅ ) ₂ C
l of n-heptane solution and 1.5 mmol of V (acetylacetonato) ₃ toluene solution were added, and the polymerization was started with stirring. The polymerization of propylene was performed at -78 ° C for 3 hours. Then, except that the reaction conditions were set at 0 ° C. for 3 hours,
Reaction with MACl was carried out in the same manner as in Example 1 to obtain a terminal-modified polypropylene having the properties shown in Table 1.

[0027]Example 4  After using acrylic acid chloride instead of MACl
Outside is an example1The reaction was carried out in the same manner as in
Was obtained. Infrared absorption of this polymer
1705 cm after measuring the yield spectrum (IR)
^-1Shows a peak based on the carbonyl group of -COOH.
Was done. Furthermore, as a result of NMR analysis, due to polypropylene
Besides the peak (δ = 0.7 to 1.7 ppm)
The peak consisting of the chemical shift value was observed.

Embedded image Further, as a result of ¹³ C-NMR analysis, a peak due to carbon of the COOH group was observed at 175 ppm. From the results of the above NMR, it was found that the acrylic acid unit was bonded to the terminal of the polypropylene. Also, from the area ratio of the carbon signal of the polypropylene part and the carbon signal of the COOH group of the acrylic acid unit, it was confirmed that three acrylic acid units were bonded to the end of the polypropylene chain.

[0028]Example 5 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 (C_TwoH_Five) _TwoCl
n-Heptane solution and 1.5 mmol of V (2-methyl
-1,3-butanedionato)_ThreeAdd the toluene solution of
Was. Next, after the pressure in the system was reduced to 680 mmHg,
Mixed gas of ethylene and propylene (40/60 molar ratio)
Is supplied continuously, and random
The polymerization was carried out at -60 ° C for 2 hours. Then, MAC15
Add 00 mmol at -60 ° C and react at the same temperature for 2 hours
I let it. Hereinafter, processing was performed in the same manner as in Example 1, and the properties shown in Table 1 were obtained.
Terminal-modified ethylene-propylene random copolymer
Obtained. Of the resulting copolymer¹³C-NMR measurement was performed, and
Peak (S) attributed to tertiary carbon and
Of propylene based on the area of
We calculated the weight. As a result, the propylene content in the copolymer was
The weight was 51.6 mol%. Propylene content (mol%) = {T / 1/2 (S + T)}
x100 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.

[0029]

[Table 1]

[0030]

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.

Continuation of the front page (72) Inventor Sou Ueki 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. General Research Laboratory (56) References JP-A-63-113002 (JP, A) 63-113001 (JP, A) JP-A-5-247122 (JP, A) JP-A-3-229705 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8 / 00-8/50

Claims (1)

(57) [Claims] An end-modified polyolefin obtained by modifying the terminal of a polypropylene or an ethylene-propylene random copolymer with a substituent represented by the following general formula I: Formula I [However, R represents a hydrogen atom or a methyl group. ]