JPH04178407A - Terminal reactive group-containing propylene (co) polymer and its production - Google Patents

Abstract

PURPOSE:To obtain the subject polymer, having a narrow molecular weight distribution and useful as a polymer compatibilizing agent, etc., by polymerizing propylene, etc., in the presence of a polymerization catalyst composed of a specific V compound component and an organometallic compound and successively reacting divinylbenzene and a proton donor, etc., therewith. CONSTITUTION:Propylene is (co)polymerized in the presence of a polymerization catalyst composed of a catalyst component containing a vanadium compound expressed by formula I (R<3> to R<5> are H or l-8C hydrocarbon group and they will not simultaneously be H) and an organometallic compound of group I, II or III metal of the periodic table. The resultant polypropylene (co)polymer having active terminals is then reacted with an aromatic divinyl compound expressed by formula II (the relative positions of two substituent groups attached to the benzene ring may be any of the o-, p-and m-positions) and subsequently reacted with a proton donor or a halogen to afford the objective (co)polymer expressed by formula III (R<1> is H or <=3C hydrocarbon; R<2> is H or halogen; n is 10-10000).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a propylene (co)polymer having a reactive vinyl group at its terminal and a method for producing the same.

[Prior art and problems to be solved by the invention] In polymerization methods using Ziegler-Natsuta catalysts, the resulting polypropylene polymer is crystalline and highly polymerized;
Synthesis of partially (terminally) modified polypropylene polymers is difficult due to the living nature of their active centers.

On the other hand, Natta et al. found that a system in which a vanadium chelate compound and an alkyl aluminum chloride were reacted exhibited high activity in the polymerization of propylene (J, Am, Chea+, Soc.

20, 1488 (1962)). Next, Soga et al. discovered that when propylene polymerization was carried out at low temperatures using this catalyst system, the polymerization proceeded in a living manner (Makromol, Chem, +180(5),
1359 (1979)). Furthermore, a catalyst system in which vanadium is reacted with various chelate compounds can achieve a similar living polymerization system, and the reaction using this living polymerization system can produce polypropylene containing a series of terminally modified syndiotaftic chains. It is known that synthesis is possible. For example, in JP-A-63-113001,
It is disclosed that vinyl-terminated polypropylene can be obtained by adding a conjugated or non-conjugated diolefin compound to a propylene living polymerization reaction system.

However, in this modification reaction, only the vinyl group connected to the aliphatic group is introduced at the end of polypropylene.
The polymerization reactivity of its terminal groups is not high. This terminal vinyl group-modified polypropylene is mainly limited to use in substitution reactions, addition reactions, etc., and is difficult to utilize as a macromonomer for vinyl polymerization. In addition, in JP-A No. 63-113002, living polymerization system of propylene (alkyl substitution)
By reacting styrene, the terminal (alkyl substitution)
It is disclosed that polypropylene modified with phenyl groups can be synthesized. However, in this polymer, unless the substituted benzyl group at the end is further treated with a modification reaction, etc.
Reactive groups cannot be introduced.

The present invention is a syndiotough propylene (co)polymer in which only the terminals of all polymer chains have polymerizable styrenic vinyl groups (1 m), have a molecular weight close to monodisperse, and are soluble in various solvents. The purpose is to synthesize.

In the conventional terminal modification reaction using the living polymerization method of propylene, conjugated/nonconjugated aliphatic diolefins and alkyl-substituted styrene are reacted, and the remaining terminal groups have low reactivity, and are converted to styryl, which has high polymerization reactivity. No modification reactions such as groups were performed.

[Means to solve the problem]

As a result of intensive research to solve the above problems, the present inventors found that
By reacting an aromatic divinyl compound with the propylene (co)polymer having a living terminal obtained by the above method, a propylene (co)polymer having a vinyl group capable of radical, anionic and cationic polymerization reactions at the terminal is produced. The present invention was completed based on the discovery that it is possible to synthesize the following.

That is, the present invention provides terminal reactive group-containing propylene (co) characterized by having a polymerization reactive group represented by the following formula (1) at one end of a propylene polymer chain or copolymer chain. It provides a polymer.

Particularly preferred as the propylene (co)polymer of the present invention is a compound represented by the following formula (II).

(However, R1 is a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms, R2 is a hydrogen atom or a halogen atom, and n is 10 to i
Indicates an integer o, ooo, substituent in phenyl group -
CH= The relative positions of CH2 are o-, m-.

Either p- position. ) Such terminal reactive group-containing propylene (co) of the present invention
The polymer is represented by formula (III) (in the formula, R3-R5 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, but all three cannot be hydrogen atoms at the same time). Polymerization or copolymerization of propylene in the presence of a polymerization catalyst consisting of a catalyst component containing a vanadium compound and an organometallic compound of a metal from Group 1, Group 1I, or Group 1II of the Periodic Table, and having an active terminal obtained by polymerizing or copolymerizing propylene. The polypropylene (co)polymer is represented by formula (IV) (however, the relative positions of the two substituents attached to the benzene ring are 0
Any position between the +lIl+p- position is acceptable. ) and then a proton donor or halogen.

The manufacturing method of the present invention will be explained in more detail below.

1111 The polymerization catalyst used in the present invention has the above-mentioned formula (III)
It consists of a catalyst component (a) containing a vanadium compound represented by and an organometallic compound (b) of a metal of Group 1, Group 1I or Group 1II of the Periodic Table.

Among the vanadium compounds represented by formula (III) above, the following compounds are particularly desirable.

Furthermore, a solid catalyst component in which these vanadium compounds are supported on a metal oxide such as silica may also be used. The solid catalyst component is produced by, for example, reacting silica with a halogenated silicon compound such as chloromethylphenethyltrichlorosilane, and reacting the obtained solid product with an organic alkali metal compound such as sodium 1,3-butanedionate. Furthermore, it can be prepared by reacting a vanadium compound.

Group 1, 1 of the periodic table used with catalyst component (a)
Organometallic compound of Group I or Group 1II metal (b)
Examples include organic compounds of lithium, magnesium, calcium, zinc or aluminum, in particular dimethylaluminum chloride, diethylaluminium chloride, diethylaluminum bromide, diisobutylaluminum chloride, etc. of the general formula R2AIX (where R is 1 carbon number ~8 alkyl group or aryl group, X
indicates a halogen atom. ) is preferable.

Living propylene polymerization method A living propylene (co)polymer is obtained by polymerizing propylene in the presence of the above polymerization catalyst. During polymerization of propylene, it is also possible to coexist a small amount of ethylene or an α-olefin such as 1-butene, 1-hexene, or 4-methyl-1-pentene.

The polymerization reaction is preferably carried out in a solvent that is inert to the polymerization reaction and is liquid at the time of polymerization, such as saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, etc. Examples include saturated alicyclic hydrocarbons such as cyclopropane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene.

The amount of polymerization catalyst used in the polymerization of propylene is 1X10-' to 0.1 mole of the vanadium compound, preferably 5X10-' to 5X10-" mole, and preferably 5X10-' to 5X10-" mole of the organometallic compound, per mole of propylene or propylene and a small amount of comonomer. 1X10-3 to 1 mol, preferably 5X10-3 to 0.
It is 1 mole. In addition, per mol of vanadium compound,
The organometallic compound is desirably 5 to 25 moles.

Living polymerization is usually carried out at -100°C to 0°C for 0.5 hours or more.
Do it for 50 hours. The molecular weight and yield of the living propylene (co)polymer obtained are determined by the amount of the polymerization catalyst used above, and
It 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 monodisperse can be obtained.

Below -65°C, Mw (weight average molecule it) /
It can be a living polymer having Mn (number average molecule it) of 1.05 to 1.40.

During the polymerization reaction, anisole, water, oxygen, alcohol (methanol, ethanol, isopropanol, etc.), and ester (benzoate, ethyl acetate, etc.) can be used as a reaction accelerator.

The amount of accelerator used is usually 0.1 to 2 mol per mol of vanadium compound.

By the above method, living propylene (co) having a number average molecular weight of about 500 to 400,000 and close to monodisperse
Polymers can be produced.

The aromatic divinyl compound to be reacted with the living propylene (co)polymer is a compound represented by the above formula (IV).

The above formula (IV) represents a conjugated aromatic divinyl compound of o-'-, m- or p-divinylbenzene.

The reaction between the living propylene (co)polymer and the aromatic divinyl compound is preferably carried out by adding the aromatic divinyl compound to the reaction system obtained in the previous step or in which the pingpropylene (co)polymer is present. The reaction is -100°C
The reaction is carried out at ~0°C for 5 minutes to 10 hours, preferably at the same temperature as the living polymerization temperature of propylene in the first stage.

The aromatic divinyl compound is used in an amount of 1 to 1.000 mol per 1 mol of the living propylene (co)polymer, but preferably living propylene (co)polymer.
A desirable range is 1 to 20 moles per mole of the polymer.

According to the method of the present invention, after the living propylene (l 1 conjugate is added to one vinyl group of divinylbenzene,
It is considered that highly active vinyl groups can be introduced at the terminals because the delocalization of the generated anions significantly reduces the reactivity of the remaining vinyl groups toward anions.

Propylene (propylene) having a polymerizable reactive group at the terminal of the present invention can be prepared by reacting a living propylene (co)polymer with an aromatic divinyl compound and then contacting it with a proton donor or halogen. A co)polymer is obtained.

Examples of the proton donor include alcohols such as methanol and ethanol, and mineral acids such as hydrochloric acid and sulfuric acid. Furthermore, examples of the halogen include iodine and chlorine. These proton donors or halogens are used in a molar range of 10 to 10,000 times the amount of the added organometallic compound,
Preferably, the range is 100 to 1000 times the mole.

Contact with a proton donor or halogen is usually -100
It is carried out for 1 minute to 10 hours at °C to +100 °C.

〔Effect of the invention〕

The terminal reactive group-containing propylene (co)polymer of the present invention is
Because living polymerization is used, the molecular weight distribution is very narrow (
Mw/Mn=1.05 to 1.40), and has a styrenic vinyl group with high addition reaction and polymerization reactivity at the chain end of the (co)polymer.

Such polymers can be used as radical polymerizable and ionic polymerizable propylene macromonomers, intermediates for block polymers using vinyl groups, and intermediates for functional group modification by vinyl modification. Examples of their applications include: Compatibilizer for polymers, light/laser curable plastics,
Examples include viscosity index improvers and substance surface modifiers.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 1 pin of propylene 10100 (1 flask) which was sufficiently purged with nitrogen gas,
200 ml of toluene was added and cooled to -78°C, and 12.6 g (300 mmol) of propylene was added at the same temperature to obtain a toluene solution of propylene. Next, 6.2
5m1. (50 mmol) of AI (C2H5) 2
C1 and 1.75 g (5.0 mmol) of (vanadium-acetylacetonate) were dissolved in 30 ml of toluene. The solution was added, and polymerization was carried out at -78°C for 1 hour with stirring.

Divinyl 2.9ml (20ml) of 1-divinylbenzene is added to the above reaction system.
mmol) and stirred at -78°C for 30 minutes.

The polymerization of the polymer was then brought into contact with 10,100O methanol at the same temperature to terminate the polymerization, and the resulting polymer was washed three times with 10,100O methanol at room temperature and dried at room temperature and under reduced pressure (yield: 2. 5g).

No ethyl acetate soluble portion was observed in this polymer, and it also contained no gel component, and it was confirmed that no divinylbenzene homopolymer or crosslinked product was produced.

The above polymer is soluble in toluene, cyclohexane, hexane, etc., and absorption based on phenyl groups was observed around 1600 cm-'.

In addition, when its molecular weight was measured by GPC analysis (polystyrene equivalent), Mn=3500 (MW/Mn=
1.2).

Furthermore, as a result of 'H-NMR analysis, in addition to the methyl, methylene, and methine signals (polypropylene backbone proton signals) at δ = 0.7 to 1.7 ppm, there was a benzene ring at δ - 7.2 ppm. Proton, vinyl group (
Signals attributed to styrenic vinyl groups) were observed.

From the comparison of the area values of the proton signal of the polypropylene part and the proton signals of the benzene ring and vinyl group,
The benzene ring and the vinyl group were present in equimolar amounts, and the molecular weight determined from the ratio of the benzene ring to the polypropylene portion was Mn = 3200. This value almost agrees with Mn=3500 determined by GPC measurement. Therefore, it was confirmed that the obtained polymer was a propylene polymer having the following formula in which one styryl group was introduced at the end of all polypropylene chains.

(n is average value 76) Example 2 Using 25.2 g (600 mmol) of propylene,
Living polymerization of propylene was carried out in the same manner as in Example 1, except that the polymerization time was changed to 3 hours, and the polymer was further treated in the same manner as in Example 1 to obtain a polymer (yield: 5.0 g).

The obtained polymer had an Mn of 25,000 and a MW/Mn of 1.3 (GPC measurement), and was confirmed to be a propylene polymer having the following formula.

(n is average value 590) Example 3 Using 25.2 g (600 mmol) of propylene,
The reaction was carried out in the same manner as in Example 1, except that the polymerization time was 3 hours and the aromatic divinyl compound to be reacted with the terminal end of the living polypropylene was p-divinylbenzene. A polymer was obtained (yield 5.0 g).

The obtained polymer had Mn of 26,000 and Mw/Mn of 1.3 (GPC measurement), and was confirmed to be a propylene polymer having the following formula.

Applicant's agent Kaoru Furutani (3 other people)

Claims (1)

[Scope of Claims] 1. Propylene containing a terminal reactive group, characterized in that it has a polymerization-reactive group represented by the following general formula (I) at one end of a propylene polymer chain or copolymer chain ( Co)polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) 2. The propylene (co)polymer according to claim 1, which is a compound represented by general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (However, R^1 is a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms, R^2 is a hydrogen atom or a halogen atom, and n is 10
It represents an integer of ~10,000, and the relative position of the substituent -CH=CH_2 in the phenyl group is any of the o-, m-, and p- positions. ) 3. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, R^3 to R^5 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, In the presence of a polymerization catalyst consisting of a catalyst component containing a vanadium compound represented by , propylene is polymerized or copolymerized, and the resulting polypropylene (co)polymer with active terminals is expressed by the general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (However, the 2 attached to the benzene ring The relative positions of the two substituents are o
It may be at any of the -, m-, and p-positions. 2. The method for producing a propylene (co)polymer according to claim 1, characterized in that the propylene (co)polymer is reacted with an aromatic divinyl compound represented by the following formula, and then with a proton donor or a halogen.