JP3319780B2 - Terminally modified polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a terminal-modified polyolefin.
More specifically, the present invention relates to a terminal-modified polyolefin having a polymer terminal modified with a primary amino group.
And its manufacturing method .

[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. It is difficult.

[0003]

In the polymerization of .alpha.-olefins with a conventional Ziegler-Natta type catalyst, a chain transfer reaction and a termination reaction occur. Therefore, even if an attempt is made to modify the terminal of the polymer, only a very small portion is modified. Therefore, the present invention introduces a primary amino group into a polymer terminal by using a living polymerization catalyst that does not involve a chain transfer reaction or a termination reaction, so that only the terminal of the polypropylene or the ethylene-propylene random copolymer has a primary amino group. Group modified end
It is an object of the present invention to provide a modified polyolefin and a method for producing the same.

[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. To methacrylic acid (acrylic acid) chloride and then to an alkylenediamine to accomplish the object of the present invention, thereby completing the present invention.

[0005]Summary of the Invention  That is, the present inventionAccording to the first aspect of the invention,Polypropylene
Of ethylene or ethylene-propylene random copolymerPieceEnd
But, By addition reactionThe following general formulaIIWith a substituent represented by
Denatured,Number average molecular weight of 500-500,00
0'sTerminally modified polyolefin, general formulaII

Embedded image Wherein R is a hydrogen atom or a methyl group and m is 2 to 6
And n represents a number of 0.1 to 100 . Is provided
You . Further, according to the second invention of the present invention, the first invention
The following general formula III

Embedded image [Wherein, R ^{1 to} R ³ represent a hydrogen atom or a carbon atom having 1 to 8 carbon atoms.
Shows a hydride group. Provided that at least one of R ^{1 to} R ³ is
It must be a hydrogen atom, but all of R ^{1 to} R ³ are hydrogen
Must not be an atom. ] Vanadium compound represented by
In the presence of a catalyst consisting of a product and an organoaluminum compound,
Living polypropylene obtained by polymerizing propylene
Or obtained by random copolymerization of ethylene and propylene
Living ethylene-propylene random copolymer
With the following general formula IV

Embedded image (Wherein, R has the same meaning as described above.)
After reacting with phosphoric acid (acrylic acid) chloride,
Terminally modified poly (ethylene glycol) characterized by reacting with diamine
A method for producing a olefin is provided .

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 and m have the same meaning as described above, and n is 0.1
Represents the number of ~ 100)

The terminal-modified polyolefin of the present invention is represented by 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 not all of R ^{1 to} R ³ must 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. To give a terminal-modified polyolefin having a (meth) acrylic acid chloride unit at the polymer end, and reacting the polymer with an alkylenediamine.

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

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

Embedded image

Embedded image

Embedded image

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

The 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 (eg, methanol, ethanol, isopropanol), esters (eg, ethyl benzoate, ethyl acetate). The amount of the accelerator used was vanadium compound 1
It is usually 0.1 to 2 mol per mol. By the above method, living polypropylene having a number average molecular weight of about 500 to about 500,000 and nearly monodisperse can be produced.

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

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

At the time of the polymerization reaction, a reaction accelerator can be used. Reaction accelerators include anisole, water, oxygen,
Examples include alcohols (eg, methanol, ethanol, isopropanol), esters (eg, ethyl benzoate, ethyl acetate). The amount of the accelerator used was 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 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.

Methacrylic acid (acrylic acid) chloride and
Reaction of living polypropylene or ethylene-propylene random copolymer with methacrylic acid (acrylic acid)
Chloride (hereinafter, referred to as compound I) has the general formula IV:

Embedded image 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 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 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 ratio of the polyolefin terminal with the compound I unit can be increased.
Compound I is based on 1 mol of living polyolefin.
1 to 1,000 mol is used.

A reaction product of a living polypropylene or a random copolymer of ethylene and propylene with the compound I is then reacted with an alkylenediamine to obtain the terminal-modified polyolefin of the present invention. Examples of the alkylenediamine include ethylenediamine, pentamethylenediamine, and hexamethylenediamine. The alkylenediamine is used in an amount of 2 to 1 per mole of the above reactant.
It is used in an amount of 00 mol. The method of contacting the above-mentioned reactant with the alkylenediamine can be arbitrarily selected, but the above-mentioned reactant is precipitated and isolated in an aproton-donating organic solvent such as acetone or ethyl acetate. It is desirable to add an alkylenediamine to a solution redissolved in a solvent such as toluene.
This reaction is usually carried out at -100 ° C to + 100 ° C for 1 minute to 1 hour.
Performed for 0 hours.

The polyolefin of the present invention obtained as described above has a number average molecular weight (Mn) of about 500 to about 500,000, and follows the living polypropylene or the ethylene-propylene random copolymer itself. Very narrow molecular weight distribution (Mw / Mn = 1.05-1.
40) and their terminals are 0.1 to 100
, Preferably 0.2 to 50, more preferably 0.1 to 0.5.
Modified with 3 to 25 of the above general formula I units.
One characteristic of the terminal-modified polypropylene 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 standard monodisperse polystyrene sample manufactured by Tosoh Corporation, and a calibration curve of polypropylene was prepared from the calibration curve by the universal method. · Structure Determination ⁽¹ H-NMR spectrum) of the polymer: manufactured by JEOL Ltd. GSX-4
00 (trade name), measured using a Fourier transform MMR spectrometer under the conditions of 400 MHz, 30 ° C., and pulse interval of 15 seconds. The sample was prepared by dissolving in deuterated chloroform. ( ^13C -NMR spectrum): XL-200 manufactured by Varian with a PFT pulse Fourier transform device.
Using a mold (trade name), 50 MHz, 120 ° C., pulse width 8.2 μs π / 3, pulse interval 4 seconds, integration number 5,000
The measurement was performed under the condition of 0. The sample was prepared by dissolving in a mixed solvent of trichlorobenzene and benzene (2: 1).

[0023]Example 1 15 ml into a 200 ml flask sufficiently purged with nitrogen gas
Limol of Al (C_TwoH _Five)_TwoCl n-heptane solution
After cooling to −60 ° C., 1.5 mmol
V (2-methyl-1,3-butanedionato)_ThreeTorue
Solution was added. Then n-hepta cooled to -60 ° C
100 ml of propylene and 100 mmol of propylene,
The polymerization was started with stirring. Polymerization of propylene to -60
C. for 1 hour. Then, methacrylic acid chloride (M
(ACl) 50 mmol are added at -60 ° C and 1
After reacting for a period of time,
The reaction solvent was poured to precipitate a polymer.

The obtained polymer was dissolved in 50 ml of tetrahydrofuran, and solid matter was removed by centrifugation. After that, 5 ml of ethylenediamine was added, and the mixture was stirred under reflux for 2 hours. Thereafter, this solution was poured into 500 ml of acetone to precipitate a polymer, and 500 ml of acetone was used to precipitate the polymer.
It was washed twice and dried at room temperature to obtain 1.57 g of a polymer.
The GPC outflow curve of the obtained polymer was monomodal.
Mn of this polymer is 3.5 × 10 ³ , and Mw / M
n was 1.12, a value close to monodispersion. Of this polymer
As a result of ¹ H-NMR analysis, a peak having the following chemical shift value was observed in addition to the peak (δ = 0.7 to 1.7 ppm) attributed to polypropylene.

Embedded image Attribution Chemical shift (Ppm: TMS standard) (a) 2.5 (b) 3.3 (c) 2.9

From the above results, it was found that a methacrylamide unit was bonded to the terminal of the polypropylene. Also, from the area ratio between the proton signal of the polypropylene part and the proton signal (c) of the methacrylamide derivative unit, it was confirmed that four methacrylamide units were bonded to the ends of the polypropylene chain as shown below. Was done.

Embedded image

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, 10 mmol of Al (C
₂ H _{5) 2} Cl in n- heptane solution and 1.0 mmol of V (2-methyl-1,3-butanedionate) ₃ in toluene was allowed to mixed solution was added in advance -60 ° C. and
The polymerization was started with stirring and continued for 10 hours. Then, 400 mmol of MACl was added at the same temperature, then 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.

[0027]Example 3 15 ml into a 200 ml flask sufficiently purged with nitrogen gas
Limol of Al (C_TwoH _Five)_TwoCl n-heptane solution
After cooling to −78 ° C., 1.5 mmol
Of V (acetylacetonate)_ThreeA toluene solution was added.
Then 100 ml of toluene cooled to -78 ° C and
Add 200 mmol of propylene and start polymerization with stirring
did. The polymerization of propylene was performed at -78 ° C for 3 hours.
Then, the reaction conditions were changed to 0 ° C. for 2 hours.
Reaction with MACl was carried out in the same manner as in Example 1.
End modified polypropylene was obtained.

Example 4 A reaction was carried out in the same manner as in Example 1 except that acrylic acid chloride was used instead of MACl, to obtain a terminal-modified polypropylene having the properties shown in Table 1.

Example 5 500 ml of toluene was placed in a 1.0 liter autoclave sufficiently purged with nitrogen gas, cooled to -60 ° C., and then a solution of 15 mmol of Al (C ₂ H ₅ ) ₂ Cl in n-heptane and 1.5 mmol of V (2-methyl-1,3
-Butandionato) A solution in which a ₃ toluene solution was previously mixed at -60 ° C was added. Next, the inside of the system is 680 mm
After reducing the pressure to Hg, a mixed gas of ethylene and propylene (40/60 molar ratio) was continuously supplied, and copolymerization of ethylene-propylene was performed at -60 ° C for 2 hours. Then, 400 mmol of MACl was added at -60 ° C, and reacted at the same temperature for 2 hours. Thereafter, the same treatment as in Example 1 was performed to obtain a terminal-modified ethylene-propylene random copolymer having the properties shown in Table 1.

The obtained copolymer was subjected to ¹³ C-NMR measurement, and the area of the peak (S) attributed to the secondary carbon and the peak (T) attributed to the tertiary carbon were determined based on the following formula. The content was calculated. As a result, the propylene content in the copolymer was 53.2 mol%. Propylene content (mol%) = [T / {(T + S) / 2}]. Times.100 As a result of thermal analysis of this copolymer by a differential scanning calorimeter (DSC), the glass derived from the propylene homopolymer was obtained. No transition temperature (about −10 ° C.) was observed.

[0031]

[Table 1]

[0032]

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 Satoshi Ueki 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. Research Institute (56) References JP-A-52-112689 (JP, A) JP-A-63-113002 (JP, A) JP-A-4-45105 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (2)

(57) [Claims] 1. A polypropylene or ethylene - one end of the propylene random copolymer becomes modified with a substituent represented by the following general formula II by an addition reaction, number average
A terminal-modified polyolefin having a molecular weight of 500 to 500,000 . Formula II Wherein R is a hydrogen atom or a methyl group and m is 2 to 6
And n represents a number of 0.1 to 100 . ] 2. A compound represented by the following general formula III : [Wherein, R ^{1 to} R ³ represent a hydrogen atom or a carbon atom having 1 to 8 carbon atoms.
Shows a hydride group. Provided that at least one of R ^{1 to} R ³ is
It must be a hydrogen atom, but all of R ^{1 to} R ³ are hydrogen
Must not be an atom. ] Vanadium compound represented by
In the presence of a catalyst consisting of a product and an organoaluminum compound,
Living polypropylene obtained by polymerizing propylene
Or obtained by random copolymerization of ethylene and propylene
Living ethylene-propylene random copolymer
With the following general formula IV : (Wherein, R has the same meaning as described above.)
After reacting with phosphoric acid (acrylic acid) chloride,
2. The method according to claim 1, wherein the reaction is carried out with a diamine.
The method for producing the terminal-modified polyolefin described in the above.