JPH05194633A - End-modified polyolefin - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to provide a polyolefin in which only terminals of polypropylene or an ethylene-propylene random copolymer are modified with a (meth) acrylic acid derivative unit and which is nearly monodisperse. And [Structure] The end of the polypropylene or ethylene-propylene random copolymer obtained by living polymerization is
A polyolefin modified with a silyloxy group- or hydroxyl group-containing (meth) acrylic acid derivative unit.
As this (meth) acrylic acid derivative, for example, trimethylosiloxyethyl methacrylate or 2-trimethylsiloxypropyl methacrylate is used.

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 (meth) acrylic acid derivative 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 polyolefin in which only terminals of polypropylene or an ethylene-propylene random copolymer are modified with a methacrylic acid (acrylic acid) derivative unit and which is nearly monodisperse. To aim.

[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 has been completed by finding that the object of the present invention can be achieved by reacting methacrylic acid (acrylic acid) derivative with.

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

[Chemical 2][However, R is a hydrogen atom or a methyl group, Z is C_mH_2m・
OSiR¹R²R³, C _mH_2m・ OSi (R^FourR^Five) O
SiR⁶R⁷R⁸Or C_mH_2m・ OH, R¹~ R ³, R
^Four~ R^FiveAnd R⁶~ R⁸Are the same or different carbon numbers 1-8
Alkyl group or aryl group, m is an integer of 1 to 6
Show. ] Is the gist.

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

[Chemical 3] [However, R and Z have the same meaning as described above, and n is 0.1 to 0.1.
Represents the number of 50]

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

[Chemical 4] [R ^{9 to} R ¹¹ represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. However, at least one of R ^{9 to} R ¹¹ must be a hydrogen atom, but all of R ^{9 to} R ¹¹ 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, (1) When Z is other than C _m H _2m · OH in the general formula, the general formula IV

[Chemical 5] [R and Z are as defined above. However, Z is C _m H _2m · OH
Except for. ] A methacrylic acid (acrylic acid) derivative represented by: (2) When Z is C _m H _2m · OH in the above general formula, the reaction product obtained in the above (1) is reacted with a proton donor. It can be manufactured respectively.

The catalyst (a) vanadium compound The vanadium compound used in the present invention has the general formula III:

[Chemical 6][However, R⁹~ R¹¹Has the same meaning as above. ] Is represented.
A specific example included in the above formula will be described below.・ R^TenIs a hydrogen atom, and R⁹And R¹¹Is a hydrocarbon group
If R⁹/ R¹¹: 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．・ R^TenIs a hydrocarbon group, R⁹, R¹¹One of them is water
When the other is a hydrocarbon group in the elementary atom. R^Ten/ R⁹Or R¹¹: CH₃/ CH₃, C₂H_Five/ CH
₃, CH₃/ C₂H_Five, C₂H_Five/ C₂H_Five, C₂H_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．・ R^TenIs a hydrogen atom, and R⁹, R¹¹Is hydrogen
When an atom is another hydrocarbon group. R⁹Or R¹¹: CH₃, C₂H_Five, C₆H_Five, C₆H_Five
CH₂ The following compounds are particularly desirable among these
Good

[Chemical 7]

[Chemical 8]

[Chemical 9]

(B) Organoaluminum compound The organoaluminum compound has the general formula R _n AlX
_3-n (wherein R is an alkyl group or an aryl group, X is a halogen atom or a hydrogen atom, and n is an arbitrary number within the range of 1 ≦ n <3), and examples thereof include 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 a mixture or complex compound 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 vanadium compound per 1 mol of propylene or propylene and a small amount of 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.) 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, 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 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. In this method, ethylene and propylene are added to and brought into contact with a solvent solution containing a compound and a vanadium compound.

The amount of the polymerization catalyst used is 1 × 10 ^{-4 to} 0.1 of vanadium compound per 1 mol of ethylene and propylene.
Mol, preferably 5 × 10 ^{−4 to} 5 × 10 ⁻² mol, and the organoaluminum 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 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. In the present invention, a polymer having a molecular weight distribution close to monodispersion can be obtained by setting the polymerization temperature to a low temperature, particularly -30 ° C or less, and at -50 ° C or less, Mw (weight average molecular weight) / Mn (number) A living ethylene-propylene random copolymer having an average molecular weight 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), esters (ethyl benzoate, ethyl acetate, etc.). The amount of the accelerator used is usually 0.1 to 2 mol per 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 of the copolymer becomes wider, which is not desirable. High ethylene content,
When a living copolymer having a narrow molecular weight distribution, that is, nearly monodisperse is produced, a small amount of propylene should be supplied to the polymerization system and kept for 0.1 to 1 hour before living-copolymerizing ethylene and propylene. This makes it 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 (converted to propylene, the same applies hereinafter) and being nearly monodisperse can be produced.

Reaction with methacrylic acid (acrylic acid) derivatives
Response living polypropylene or ethylene - methacrylic acid reacted with the propylene random copolymer (acrylic acid)
The derivative (hereinafter referred to as compound I) has the general formula IV

[Chemical 10] It is represented by. In the formula, R represents a hydrogen atom or a methyl group, Z ¹ is ^{_{C m H 2m · OSiR 1 R}} 2 R 3 or C
^{_{m H 2m · OSi (R 4}} R 5) OSiR 6 R 7 R 8, m represents an integer of ^{1~6, R 1 ~R 3, R} 4 ~R 5 and R ⁶
To R ⁸ are the same or different, and are alkyl groups having 1 to 8 carbon atoms or arule groups such as phenyl, tolyl and xylyl groups. Among these, especially methyl, ethyl, (n, i
An alkyl group having 1 to 4 carbon atoms such as-) propyl and (n, i, s, t-) butyl group is preferable. In addition, R ^{1 to} R ³ , R
^It is desirable that ⁴ and R ⁵ and R ^{6 to} R ⁸ are independently the same group. In addition, · OSiR ¹ R ² R ³ , · OS
i (R ⁴ R ⁵ ) OSiR ⁶ R ⁷ R ⁸
Means to bond to any carbon atom in the alkylene group of _m H _2m .

Living polypropylene or ethylene
The reaction between the ropylene random copolymer and compound I is
Polypropylene or ethylene-propylene random
Compound I is supplied to the reaction system in which the copolymer is present to react.
It is desirable to use the method. The reaction is -100 ℃ to + 150 ℃
At a temperature of 5 minutes to 50 hours. Increase reaction temperature
Or by increasing the reaction time, the compound I unit
To increase the rate of modification of the polyolefin end with
it can. Compound I is 1 mol of living polyolefin
On the other hand, 1 to 1,000 mol is used. To hide
Accordingly, Z in the general formula of the substituent is C_mH_2m・ OSiR
¹R²R ³And C_mH_2m・ OSi (R^FourR^Five) OSiR
⁶R⁷R⁸In the case of
can get.

Further, by reacting the terminal-modified polyolefin obtained above with a proton donor, the terminal-modified polyolefin of the present invention in which Z is C _m H _2m · OH can be produced. As the proton donor, alcohols such as methanol, ethanol and phenol,
Mineral acids such as hydrochloric acid and sulfuric acid may be mentioned. The alcohol and the mineral acid may be used at the same time. The proton donor is usually used in large excess. Contact with a proton donor is usually -100.
It is carried out at a temperature of from ℃ to +100 ℃ 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) and each end is 0.1 to 50
Modified, preferably from 0.2 to 20 of the compound I units. Further, the terminal-modified polyolefin of the present invention is characterized in that the syndiotactic dyad fraction is 0.6 or more.

[0023]

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 ( ¹ H-NMR spectrum): JSX-4 manufactured by JEOL Ltd.
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): Using Varian XL-200 (trade name) with PFT pulse Fourier transform device, 50 MHz, 120 ° C., pulse width 8.2 μs π / 3, pulse interval 4 seconds, number of integration 5 , 0
It was measured under the condition of 00. The sample was prepared by dissolving it in a mixed solvent of trichlorobenzene and benzene (2: 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.

Example 1 Living Polymerization of Propylene In a 300 ml flask sufficiently replaced with nitrogen gas, n-
100 ml of heptane was added and cooled to -60 ° C. 200 mmol of propylene was added at the same temperature and dissolved in n-heptane. Then 15 mmol of Al (C ₂ H ₅ ) ₂ C
An n-heptane solution and a 1.5 mmol V (2-methyl-1,3-butanedionate) ₃ toluene solution were added, and the polymerization was initiated with stirring. Polymerization of propylene-
It was carried out at 60 ° C. for 1 hour.

Trimethylsiloxyethyl methacrylate
Reaction with trimethylsiloxyethyl methacrylate (HEMA-Si) (100 mmol) was added to the above reaction system at -60 ° C, and the temperature in the system was raised to 25 ° C over 1 hour.
HEMA-Si was polymerized at the same temperature. After 5 hours, 5
The reaction solution was put into 00 ml of ethanol to precipitate a polymer. The obtained polymer was washed 5 times with 500 ml of methanol and further dried at room temperature to obtain 0.86 g of a polymer. The GPC efflux curve of the resulting polymer was unimodal. Mn of this polymer was 2.7 × 10 ³ , and Mw / Mn was 1.15, which was a value close to monodispersion.
When IR analysis of this polymer was carried out, a peak based on carbonyl absorption was observed at 1740 cm ^-1 . Also, 3450
A peak due to the absorption of a broad hydroxyl group was observed near cm ^-1 , but no absorption of a trimethylsilyl group was observed. Furthermore, as a result of ¹ H-NMR analysis, a peak attributable to polypropylene (δ = 0.7 to 1.7 pp
In addition to m), peaks having the following chemical shift values were observed. Further, the methyl proton of the trimethylsilyl group was not seen.

[Chemical 11] Proton signal of polypropylene part (δ = 0.7 ~
1.7 ppm) and the proton signal of the above substituent (c)
From the area ratio of 1, it was confirmed that one of the above substituent units was bonded to the end of the polypropylene chain.

From the above results, the reaction product obtained by reacting living polypropylene with HEMA-Si before contacting with ethanol is a polymer in which one of the following substitution units is bonded to the end of the polypropylene chain. Is estimated to be

[Chemical 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 obtained polypropylene was mixed with ¹³ C-
NMR 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] 0.627 0.317 0.056 0.786 a) Calculated from the triad fraction

Examples 2 and 3 Terminal-modified polypropylene was obtained in the same manner as in Example 1 except that the polymerization conditions for propylene and the reaction conditions for HEMA-Si were as shown in Table 1. The results are shown in Table 1.

Example 4 400 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 15 hours. .. Then, at the same temperature, HEMA-S
i500 mmol was added and the reaction with HEMA-Si was carried out at -60 ° C for 10 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 5 In a 300 ml flask sufficiently replaced with nitrogen gas, n-
100 ml of heptane was added and cooled to -78 ° C. 200 mmol of propylene was added at the same temperature, and liquefied and dissolved in n-heptane. Then, 15 mmol of Al (C
_{A 2} H ₅ ) ₂ Cln-heptane solution and a 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, a reaction with HEMA-Si was carried out in the same manner as in Example 1 except that the reaction conditions were changed as shown in Table 1 to obtain a terminal-modified polypropylene having the properties shown in Table 1.

Example 6 In Example 1, 2-trimethylsiloxypropyl methacrylate (HPMA-S was used instead of HEMA-Si.
A polymer was obtained in the same manner as in Example 1 except that i) was used and the reaction conditions were as shown in Table 1. When IR analysis of this polymer was carried out, a peak due to carbonyl absorption was observed at 1740 cm ^-1 . A peak due to the absorption of a broad hydroxyl group was observed at around 3450 cm ^-1 , but no peak due to the absorption of a trimethylsilyl group was observed. Furthermore, as a result of ¹ H-NMR analysis, it was confirmed that the obtained polymer had one of the following substituent units bonded to the end of polypropylene.

[Chemical 13]

From the above results, the reaction product obtained before the contact between the living polypropylene and HPMA-Si by contacting with ethanol was obtained by adding 1 to the end of the polypropylene chain.
It is presumed to be a polymer in which the following substituted units are bonded.

[Chemical 14]

[Table 1]

Example 7 Synthesis of Living Ethylene-Propylene Random Copolymer 250 ml of n-heptane was placed in a 500 ml autoclave sufficiently substituted with nitrogen gas, cooled to -60 ° C, and then 15 mmol of Al (C _A solution of ₂ H ₅ ) 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 the pressure inside the system was reduced to 700 mmHg, a mixed gas of ethylene and propylene (40/60 molar ratio) was continuously supplied to carry out ethylene-propylene copolymerization by -6.
It was performed at 0 ° C. for 1 hour to synthesize a living ethylene-propylene random copolymer (hereinafter, ethylene-propylene random copolymer is referred to as EPR). On the other hand, in order to measure the molecular weight, molecular weight distribution and propylene content of the ethylene-propylene copolymer part, ethylene and propylene were copolymerized by the same method as described above to obtain 1.83 g of EPR. Mn of the obtained copolymer was 6.8 × 10.
³ , Mw / Mn was 1.21. Furthermore, ¹³ C-NMR measurement of this 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 52.7.
It was mol%. Propylene content (mol%) = {T / 1/2 (S + T)}
× 100 The glass transition temperature (about -10 ° C) attributable to the propylene homopolymer was not observed as a result of thermal analysis of this copolymer by a differential scanning calorimeter (DSC).

Trimethylsiloxyethyl methacrylate
Reaction with and to the above reaction system, 250 mmol of trimethylsiloxyethyl methacrylate (HEMA-Si) was added at the same temperature, the temperature in the system was raised to 0 ° C. over 1 hour, and then stirred at the same temperature. Reaction with HEMA-Si was performed. After 5 hours, the reaction solution was put into 500 ml of methanol to precipitate a polymer. The polymer obtained was washed 5 times with 500 ml of methanol and then dried under reduced pressure at room temperature to give 1.
85 g of polymer was obtained. The GPC efflux curve of the resulting polymer was unimodal. The Mn of this polymer is 6.8 ×
It was 10 ³ , and Mw / Mn was 1.22, which was a value close to monodispersion. When IR analysis of this polymer was conducted, it was found to be 17
Absorption due to carbonyl stretching vibration was observed at 40 cm ^-1 . In addition, absorption of a broad hydroxyl group was observed near 3450 cm ^-1 , but absorption of a trimethylsilyl group was not observed. Furthermore, as a result of ¹ H-NMR analysis, a peak (δ = 0.7
In addition to (-1.7 ppm), peaks having the following chemical shift values were observed. No peak attributed to the methyl proton of the trimethylsilyl group was observed.

[Chemical 15] Proton signal of EPR part (δ = 0.7 to 1.7 p
pm) and the area ratio of the signal (c), the propylene content and the molecular weight of the EPR, the obtained polymer was obtained by introducing the two substituent units at the end of the EPR as described below. It turned out to be. From the above results, the reaction product obtained by the reaction between living EPR and HEMA-Si before contact with methanol was EP
It is presumed to be a polymer in which the following two substitution units are bonded to the end of the R chain.

[Chemical 16]

Example 8 Ethylene-propylene copolymerization conditions and HEMA-S
Example 7 except that the reaction conditions for i were as shown in Table 2.
A terminal-modified EPR was obtained in the same manner as in. Separately from this, ethylene and propylene were copolymerized by the same method as above to obtain 3.72 g of EPR. M of this copolymer
n was 13.0 × 10 ³ , Mw / Mn was 1.21, and the propylene content was 56.2 mol%.

[0035]Example 9 1.5 liter autoclave fully replaced with nitrogen gas
Put 800 ml of n-heptane into the flask and cool to -60 ° C.
After that, 1.5 g of propylene was added at the same temperature, and n-hep
It was liquefied and dissolved in tongue. Then 40 mmol A
l (C₂H_Five) ₂Cl in n-heptane and 0.8 M
Limol V (2-methyl-1,3-butanedionate)₃
A toluene solution was added, and the mixture was stirred at -60 ° C for 10 minutes.
Next, after reducing the pressure in the system to 680 mmHg,
Continuous mixed gas of propylene and propylene (50/50 molar ratio)
Supplied ethylene-propylene copolymer at -60 ° C
At room temperature for 10 hours to synthesize living EPR. Next
Then, 500 mmol of HEMA-Si was added at the same temperature.
Then, the temperature of the reaction system was raised to -40 ° C over 1 hour,
The reaction with HEMA-Si was carried out for 15 hours. The following
The same treatment as in Example 7 was carried out, and the end-modified EPR having the properties shown in Table 2 was used.
Got On the other hand, ethylene and propylene are treated in the same manner as above.
Copolymerization was performed to obtain 23.9 g of EPR. This
Mn of polymer is 101.4 × 10³, Mw / Mn is
1.26, the propylene content was 48.6 mol%
It was

Example 10 250 ml of toluene was put into a 500 ml autoclave sufficiently replaced with nitrogen gas, cooled to -78 ° C., and then 15 mmol of Al (C ₂ H ₅ ) ₂ Cl solution in n-heptane and A 1.5 mmol V (acetylacetonato) ₃ toluene solution was added. Next, 700 in the system
After reducing the pressure to mmHg, a mixed gas of ethylene and propylene (40/60 molar ratio) was continuously supplied, and ethylene-propylene copolymerization was performed at -78 ° C for 3 hours to synthesize a living EPR. Then, at the same temperature, HEMA-S
After i250 mmol was added, the temperature of the reaction system was raised to −20 ° C. over 1 hour, and the reaction with HEMA-Si was performed for 1 hour. Thereafter, the same treatment as in Example 7 was carried out to obtain a terminal-modified EPR having the properties shown in Table 2. On the other hand, copolymerization of ethylene and propylene was carried out in the same manner as above to obtain 1.54
g EPR was obtained. Mn of this copolymer was 8.7 × 10.
³ , Mw / Mn is 1.26, propylene content is 3
It was 7.6 mol%.

Example 11 In Example 7, 2-trimethylsiloxypropyl methacrylate (HPMA- was used instead of HEMA-Si.
A polymer was obtained in the same manner as in Example 7, except that Si) was used and the reaction conditions were as shown in Table 2. When IR analysis of this polymer was carried out, absorption due to carbonyl stretching vibration was observed at 1740 cm ^-1 . Also, 345
Absorption of a broad hydroxyl group was observed at around 0 cm ^-1 , but no absorption of a trimethylsilyl group was observed. Furthermore, as a result of ¹ H-NMR analysis, it was confirmed that the polymer obtained had one of the following substitution units bonded to the end of polypropylene.

[Chemical 17] From the above results, it is presumed that the reaction product obtained by reacting living EPR with HPMA-Si before contacting with methanol is a polymer in which one of the following units is bonded to the end of the EPR chain. It

[Chemical 18]

[0038]

[Table 2]

[0039]

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. Polypropylene or ethylene-propylene
The terminal of the random copolymer is represented by the following general formula I:
An end-modified polyolefin modified with a substituent. General formula I[However, R is a hydrogen atom or a methyl group, Z is C_mH_2m・
OSiR¹R²R³, C _mH_2m・ OSi (R^FourR^Five) O
SiR⁶R⁷R⁸Or C_mH_2m・ OH, R¹~ R ³, R
^Four~ R^FiveAnd R⁶~ R⁸Are the same or different carbon numbers 1-8
Alkyl group or aryl group, m is an integer of 1 to 6
Show. ]