JPH0686482B2 - End-modified propylene polymer and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a propylene polymer end-modified with olefin and a method for producing the same.

BACKGROUND ART A polymer in which a substituent such as a functional group is bonded to a chain of a propylene polymer obtained by using a solid Ziegler-Natsuta type catalyst is known, but it is selectively present only at the end of the polymer chain. It is difficult to attach a substituent.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a propylene polymer in which only the ends of all polymer chains are modified with olefin and which is nearly monodisperse.

The present inventors have previously found that living polymerization of propylene using a soluble vanadium-based catalyst can give polypropylene close to monodisperse, but the present inventors have further added iodine to the chain end of this living polypropylene, We have developed propylene polymers modified with hydroformyl and amino groups [Makromol. Chem. 186 , 1825 (1985) .M.
akromol.Chem., Repid Commun. 5 , 811 (1984), Adu.Pol
ym.Sci. 73/74 , 201 (1986)].

The present inventors have completed the present invention by finding that a propylene polymer having a terminal modified with olefin can be obtained by reacting living polypropylene obtained by the above method with diolefin.

Means for Solving the Invention That is, the present invention includes (1) a general formula [However, n is a number of 20 to 10,000 and m is an integer of 0 to 6. ] The terminal modified propylene polymer of [In formula, R < ⁶ > -R < ⁸ > shows a hydrogen atom or a C1-C8 hydrocarbon group. However, at least one of R ^{6 to} R ⁸ must be a hydrogen atom, but all of R ^{6 to} R ⁸ must not be hydrogen atoms. ] Living propylene obtained by polymerizing propylene in the presence of a polymerization catalyst consisting of a catalyst component (a) containing a vanadium compound represented by the following formula and an organometallic compound (b) of a metal of group I to group III of the periodic table. The polymer is represented by the general formula CH ₂ ═CHCH _{2 m} CH═CH ₂ [where m is an integer of 0 to 6]. ] The process for producing a propylene polymer, which comprises reacting with diolefin and then reacting with a proton donor, is summarized.

Polymerization Catalyst The polymerization catalyst used in the present invention comprises a catalyst component (a) containing a vanadium compound represented by the following general formula and an organometallic compound (b) of a Group I to Group III metal.

General formula [However, R ^{6 to} R ⁸ are as defined above. Of the vanadium compounds included in the above general formula, the following compounds are particularly desirable.

Further, a solid catalyst component obtained by fixing these vanadium compounds to a metal oxide such as silica can also be used. The solid catalyst component is, for example, silica and a silicon halide compound such as chloromethylphenethyltrichlorosilane are reacted, and the obtained solid product is reacted with an organic alkali metal compound such as sodium 1,3-butanedionate. It can then be prepared by reacting the solid product with a vanadium compound.

Examples of the organometallic compound (b) of a Group I to Group III metal used together with the catalyst component (a) include organic compounds of lithium, magnesium, calcium, zinc and aluminum, and particularly dimethylaluminum chloride and diethylaluminum. General formula R ₂ AlX such as chloride, diethylaluminum bromide, diisobutylaluminum chloride [wherein R represents an alkyl group or aryl group having 1 to 8 carbon atoms, and X represents a halogen atom]. ] The organoaluminum compound represented by

Method for producing living propylene polymer The living propylene polymer is obtained by polymerizing propylene in the presence of the above-mentioned polymerization catalyst. When propylene is polymerized, a small amount of ethylene or 1-butene,
It is also possible to polymerize in the presence of α-olefin such as 1-hexene or 4-methyl-1-pentene.

The 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, and cyclohexane. Examples thereof include saturated alicyclic hydrocarbons such as propane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene.

The amount of the polymerization catalyst used during the polymerization of propylene is 1 × 10 ^{−4 to} 0.01 mol, preferably 5 × 10 ⁻⁴ , of vanadium compound per 1 mol of propylene or a small amount of propylene and a small amount of comonomer.
˜5 × 10 ⁻³ mol, and the organometallic compound is 1 × 10 ^{−3 to} 0.1 mol, preferably 5 × 10 ^{3 to} 0.01 mol. The amount of the organometallic compound is preferably 5 per mol of the vanadium compound.
~ 25 moles are used.

Living polymerization is usually carried out at -100 ° C to + 150 ° C for 0.5 to 50 hours.

The molecular weight and yield of the obtained living propylene polymer 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 -65 ° C or lower, w (weight average molecular weight) /
A living polymer having n (number average molecular weight) of 1.05 to 1.40 can be used.

A reaction accelerator can be used during the polymerization reaction. Examples of the reaction accelerator include anisole, water, oxygen, alcohol (methanol, ethanol, isopropanol, etc.), ester (ethyl benzoate, ethyl acetate, etc.). The amount of the accelerator used is 1 mol of the vanadium compound,
It is usually 0.1 to 2 mol.

By the above method, a living propylene polymer having a number average molecular weight of about 800 to about 400,000 and being nearly monodisperse can be produced.

Reaction with diolefin The diolefin reacted with the living propylene polymer is represented by the general formula CH ₂ ═CHCH _{2 m} CH═CH ₂ [where m is an integer of 0 to 6]. ] Is represented. Specific examples thereof include 1,3-butadiene and 1,4-
Examples include pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene and 1,9-decadiene.

The reaction between living propylene polymer and diolefin is
A method of supplying diolefin to the reaction system in which the living propylene polymer obtained in the previous stage is present and reacting it is desirable. The reaction is carried out at −100 ° C. to + 150 ° C. for 5 minutes to 10 hours, but it is desirable to carry out the reaction at a temperature close to the temperature of the living polymerization of propylene in the first stage.

The diolefin is used in an amount of 1 to 1,000 mol based on 1 mol of the living propylene polymer.

Reaction with Proton Donor The reaction product of living propylene and diolefin is then contacted with a proton donor to obtain a propylene polymer having a terminal double bond in the present invention.

Examples of the proton donor include alcohols such as methanol, ethanol and phenol, and mineral acids such as hydrochloric acid and sulfuric acid. The alcohol and the mineral acid may be used at the same time. The proton donor is usually used in large excess. The contact with the proton donor is usually performed at -100 ° C to + 150 ° C for 1 minute to 10 hours.

EFFECTS OF THE INVENTION The propylene polymer obtained as described above has a very narrow molecular weight distribution (w / n = 1.05 to 1.40) following the living propylene polymer itself, and almost all of the polymer. It is ole? Nated on the chain.

Such a polymer can be used as a macromer having a uniform molecular weight.

Hereinafter, the present invention will be described with reference to examples. The characteristics of the polymer were measured by the following equipment and method. ¹ H NMR analysis JEOL Ltd. GX-500, Fourier transform type NMR spectrometer (500 MHz, room temperature, pulse interval 5.0 seconds) GPC Showa Denko KK, SHYO-DEX LCHT-3, gel permeation chromatography (Column; Syodex 80 M, 140 ° C., solvent; o-dichlorobenzene) Example 1 Living Polymerization of Propylene In a 300 ml flask sufficiently replaced with nitrogen gas, toluene 3 was added.
8 ml was put and it cooled at -78 degreeC. 67 mmol of propylene was added at the same temperature and dissolved in toluene. Then, 10 mmol of Al (C ₂ H ₅ ) ₂ Cl toluene solution and 1.0 mmol of V (acetylacetonato) ₃ toluene solution were added, and the polymerization was started with stirring. Polymerization of propylene was carried out at -78 ° C for 1 hour.

Reaction with butadiene To the above reaction system, add 63 mmol of 1,3-butadiene,
The mixture was stirred at -78 ° C for 1 hour.

Formation of Polymer Next, the polymer was brought into contact with 300 ml of a hydrochloric acid-methanol mixed solution, the produced polymer was washed 5 times with 300 ml of methanol, and dried at room temperature under reduced pressure.

When the number average molecular weight (n) of the obtained polymer was measured by GPC, it was 2,100 and (w / n = 1.2).

In addition, the ¹ H NMR spectrum of this polymer is shown in FIGS.
As shown in the figure, the attribution is as follows.

δ (ppm) attributed 0.7 to 1.7 Proton of polypropylene part 2.1 C H ₂ -C = C (a) 5.0 C = C H ₂ (b) 5.3- H C = C H- (c) 5.8- H C = C (D) From the above results, the obtained polymer was composed of a mixture of the following two kinds of polymers (1) and (2), and from the area ratio of the peak (b) and the peak (c), the polymer (1)
Was found to be 75 mol% and polymer (2) was 25 mol%.

(The average value of n is about 50) Furthermore, the molecular weight was calculated from the area ratio of the peak (b), the peak (c) and the peak (d) with respect to the peak (δ = 0.7 to 1.7) of the polypropylene part, and n = 2,200. , Which is in good agreement with the above-mentioned measurement result by GPC. From this result, it was found that one butadiene molecule was bonded to each polypropylene chain without causing side reactions such as copolymerization and homopolymerization.

Example 2 A polymer was obtained in the same manner as in Example 1 except that 1,7-octadiene was used instead of 1,3-butadiene.

N of the obtained polymer by GPC was 2,200, and w /
n was 1.2. As a result of ¹ H NMR analysis, the peak (a) observed in the polymer obtained in Example 1
(B) and (d) were observed, but the peak (c) was not observed. From this, it was revealed that this polymer had the following structural formula.

(The average value of n is about 52.) Example 3 Living polymerization of propylene was carried out in the same manner as in Example 1 except that 830 mmol of propylene was used and the polymerization time was 3 hours. Further, the same treatment as in Example 2 was carried out to obtain a polymer.

The obtained polymer n was 15,000 and w / n was 1.1. As a result of ¹ H NMR analysis, peaks (a), (b), and (d) were observed as in Example 1. Therefore, the polymer was found to have the following structural formula:

(The average value of n is about 360)

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an NMR chart of the polymer of the present invention, and FIG. 2 is a partially enlarged view of FIG.

Claims (2)

[Claims] 1. A general formula [However, n is a number of 20 to 10,000 and m is an integer of 0 to 6. ] The terminal modified propylene polymer of. 2. General formula [In formula, R < ⁶ > -R < ⁸ > shows a hydrogen atom or a C1-C8 hydrocarbon group. However, at least one of R ^{6 to} R ⁸ must be a hydrogen atom, but all of R ^{6 to} R ⁸ must not be hydrogen atoms. ] Living propylene obtained by polymerizing propylene in the presence of a polymerization catalyst consisting of a catalyst component (a) containing a vanadium compound represented by the following formula and an organometallic compound (b) of a metal of group I to group III of the periodic table. The polymer is represented by the general formula CH ₂ ═CHCH _{2 m} CH═CH ₂ [where m is an integer of 0 to 6]. The number of reacted with diolefins, then the general formula _{CH 2 -CH 2 n CH 2 -CH} 2 CH 2 m CH = CH 2 which comprises reacting with a proton donor [where, n is 20～10,000 represented by] , M is an integer of 0 to 6. ] The manufacturing method of the terminal modified propylene polymer of this.