JPS6072909A - Production of graft copolymer - Google Patents

Abstract

PURPOSE:To obtain a graft copolymer in good efficiency, by adding an organoaluminum compound, a catalyst component containing Ti, Mg, and a halogen and an olefin to a specified olefin polymer, and polymerizing the mixture. CONSTITUTION:An organoaluminum compound is added to an olefin polymer comtaining an oxygen-containing functional group and a vinyl group, and an olefin and a catalyst component containing titanium, magnesium and a halogen are added to the mixture. The resulting mixture is reacted. As the olefin polymer containing an oxygen-containing functional group and a vinyl group, one having an MW of 1,000-5,000 is suitably used. As an organoaluminum compound, a compound of formula I or a mixture thereof with a compound of formula II is desirable. In the formulas, R<1> is alkyl or the like, and X<1> is a halogen atom. Copolymers formed by the graft copolymerization with an olefin, especially, ethylene or propylene are of industrial importance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for efficiently producing a graft copolymer by graft copolymerizing an olefin to an olefin polymer having an oxygen-containing functional group and a vinyl group.

Polyolefin resins such as polyethylene and polypropylene inherently have poor adhesion and dyeability, and in order to improve these physical properties, conventional methods have been used to graft copolymerize polar vinyl compounds onto polyolefins using a radical initiator. ing. On the other hand, as a method for graft copolymerizing an olefin to an olefin polymer, a method of copolymerizing polybutadiene and propylene using a catalyst consisting of titanium trichloride, an organoaluminum compound, a halogenated benzene, and a trialkyl-7-osphine compound ( Unexamined Japanese Patent Publication 1973
-145716) is known.

However, this method was not fully satisfactory, as the catalyst activity was low, a deashing step was required after the polymerization reaction, and the physical properties could not be sufficiently improved since no polar groups were included.

The present inventors have conducted extensive research to develop a method for producing graft copolymers that overcomes the drawbacks of conventional methods. As a result, we have achieved the desired purpose by using a specific olefin polymer and a highly active catalyst. They have found what they can achieve and have completed the present invention.

That is, in producing a copolymer grafted with an olefin, the present invention adds an organoaluminum compound to an olefinic polymer having an oxygen-containing functional group and a vinyl group, and then adds a catalyst containing at least titanium, magnesium, and a halogen. The present invention provides a method for producing a graft copolymer, which comprises adding a component and an olefin and reacting the same.

In the present invention, the olefin polymer having an oxygen-containing functional group and a vinyl group can be used without any particular restriction on molecular weight or the like. However, in general, the molecular weight is 500 to 1 O,
000, particularly i,ooo to 5,000 are preferably used. Note that examples of the oxygen-containing functional group include a hydroxyl group and a carboxyl group.

Examples include aldehyde groups and ester groups, and these are preferably bonded to both ends of the olefin polymer molecule. The content of vinyl groups in the olefin polymer is not particularly limited, but is usually 2 to 50% by weight, preferably 5 to 30% by weight of the olefin polymer. In addition, when the olefin polymer is a diene polymer such as polybutadiene, vinyl bonds (vinyl groups) account for 5 to 95% of the double bonds in the molecule, preferably 20 to 50%.
It is. Olefins such as ethylene and propylene are graft-polymerized to this vinyl group, so if the vinyl group content is too small, the graft copolymer targeted by the present invention cannot be efficiently obtained. There are no particular restrictions on the material, and a variety of materials can be used.
Examples include diene copolymers such as butadiene copolymers. In addition, the vinyl group content mentioned above refers to trans type and cis type in butadiene units.

The ratio of vinyl molds to the total vinyl molds is referred to as the proportion of vinyl molds.

Next, the olefin used in the present invention is one that is grafted and copolymerized with the above-mentioned olefin polymer, especially its vinyl group, and any compound having an ethylene bond can be used without any particular restriction, and usually General formula〇H
11=α-olefin represented by OR-R. Here, R is hydrogen, an alkyl group having 1 to 16 carbon atoms, or an aryl group.

Specifically, ethylene, propylene, butene-1゜---
--e-, x=nJ,? 4161JI"-hat sir-
Copolymers obtained by graft copolymerization of propylene and r#1/n are industrially important.

In the present invention, the catalyst used for graft copolymerization is
A solid catalyst component containing an organoaluminum compound and at least titanium, magnesium, and halogen.

The organic azminium compound has the general formula AJR"
A compound represented by X'8 is used.

1-1 In the formula, 几1 is an alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms, l is a real number between 1 to 3, and xl represents a halogen atom such as chlorine or bromine. .

Among these, compounds represented by the general formulas R'' and A! and mixtures of these compounds and compounds represented by the general formulas R' and AIX' are particularly preferred.Specifically, trimethylaluminum, triethylaluminum, triisopro'pylaluminum, triisobutyl Preferred are aluminum, trioxyaluminum compounds such as trioctylaluminum, and dialkylaluminum monohalides such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum monochloride, and also mixtures thereof. Examples of mixtures include triethylaluminum and diethylaluminum chloride.In the present invention, trimethylaluminum and diethylaluminum chloride are preferred.
Minilum and mixtures of trimethylaluminum and diethylaluminum are particularly preferably used.

Next, the catalyst component containing at least titanium, magnesium, and halogen is not particularly limited, and various types can be considered.

For example, it can be obtained by reacting a magnesium compound, which is commonly used as a carrier for Ziegler catalysts, with a titanium compound containing hagen.

Various types of magnesium compounds can be used as the above magnesium compound, but the general formula? The specific volume expressed as X", (OR")Q-U is preferred. In the formula, . is an alkyl group having 1 to 1 carbon atoms, preferably 1 to 1 o carbon atoms.

It is a cycloalkyl group, an aryl group, an aralkyl group, etc., X' is a halogen atom such as chlorine or bromine, and n is a real number between 1 and 20. Preferred specific examples of the magnesium compound include magnesium dimethoxide and diced magnesium diethoxide.

Magnesium dipropoxide, magnesium dibutoxide, magnesium dicyclohexyne oxide.

Magnesium dialkoxides such as magnesium dibenzoxide, methoxymagnesium chloride.

Examples include alkoxymagnesium halides such as ethoxymagnesium chloride and propoxymagnesium chloride, and magnesium halides such as magnesium dichloride and magnesium dichloride. Commercially available magnesium dialkoxides can be used as the above magnesium dialkoxide, but reactions between metallic magnesium and alcohol,
Those produced by the reaction of alkylmagnesium and alcohol may also be used.

Further, magnesium carboxylates such as magnesium acetate, magnesium stearate, and magnesium benzoate are also preferably used as magnesium compounds.

Next, as a titanium compound, the general formula 'I'1 (OR'')
I.

A compound represented by Xs, -0 is used. In the ceremony, T
Lll is an alkyl group, cycloalkyl group, aryl group, alkenyl group, or aralkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, X and 8 are halogen atoms such as chlorine, bromine, or iodine, and m is A real number in the range 0≦m<4, especially an integer of 0.1.2 or 3, but 1.5
It may be a real number such as, or it may be within the above range as an average value of the mixture.

Specifically, these compounds are T1014. 'I
Tetrahalogenated titanium such as '1Br4゜〒1■4,
! l'1(OCRs)O40°Ti(OO*U,)07
g, Ti(On-04B-071, Ti(OOgRs
) Br.

Nato's Shiba Tetragenated Alkoxytitanium, Ti(001
(a) a04Ti(00,H,), O7,Ti(On
Examples include monohalogenated trialkoxytitanium such as -C, E, ), (MI Ti(00sHs)sBr).These may be used alone or as a mixture.Among these, those with high halogen content are Preferably, titanium tetrachloride (Ti0j!4) is used.

It is sufficient for the catalyst component containing at least titanium, magnesium, and nitrogen to contain the above-mentioned components, but it may further contain an electron-donating compound. The electron donating compound here is an organic compound containing oxygen, nitrogen, phosphorus or sulfur. Specifically, amines,
Amides, ketones, nitriles, phosphines, phosphoramides, esters, thioethers, thioesters, alcohols, acid anhydrides, acid nolides, aldehydes.

Examples include organic acids.

More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; acid anhydrides such as succinic anhydride, benzoic anhydride, and p-)ruyl acid anhydride; acetone and methyl ethyl ketone. .

Ketones having 3 to 15 carbon atoms such as methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone;
Acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde.

2-1 carbon atoms such as tolualdehyde and naphthaldehyde
5. Aldehyde furnace; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, tepropyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, croton Ethyl acid, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate.

Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate/methyl anisate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate.

Ethyl 0-chlorobenzoate, ethyl naphthoate.

r-butyrolactone, δ-valerolactone, coumarin,
Esters with 2 to 18 carbon atoms such as phthalide and ethylene carbonate; acid halides with 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluyl acid chloride, anisyl chloride; methyl ether) L/l ethyl ether;
Ethers with 2 to 20 carbon atoms, such as isoflovir ether, n-butyether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, and ethylene glycol butyl ether; acid amides, such as acetamide, benzoic acid amide, toluic acid amide, etc. ; tributylamine, N,N'-dimethylpiperazine.

tribenzylamine, aniline, pyridine, picoline,
Ami/1i7-1 such as tetramethylethylenediamine
! ) Nitriles such as nitrile, benzonitrile, and tolnitrile; examples include tetramethylurea, nitrobenzene, and lithium butyrate. Among these, esters, ethers, ketones, acid anhydrides and the like are preferred. In particular, alkyl esters of aromatic carbons, such as benzoic acid, p-methoxybenzoic acid.

C1-C4 alkyl esters of aromatic carboxylic acids such as p-ethoxybenzoic acid and toluic acid are preferred; aromatic ketones such as benzoquinone; aromatic carboxylic acid anhydrides such as benzoic anhydride; and ethylene glycol. Ethers such as butyl ether are also preferred.

Various methods have been proposed for producing the catalyst component used in the present invention using a magnesium compound, a halogen-containing titanium compound, and an electron-donating compound as described above. Examples include a co-grinding method and a slurry method. Here, the co-pulverization method is a method in which co-pulverization is performed to a degree equivalent to pulverization using a device such as a rotary ball mill, a vibrating ball mill, or an impact mill. In this co-pulverization method, an electron-donating compound is used. (1) A magnesium compound and an electron-donating compound are co-pulverized, and the co-pulverized product and a halogen-containing titanium compound are co-pulverized or suspended in an inert solvent. (2) A method in which a magnesium compound, an electron-donating compound, and a halogen-containing titanium compound are simultaneously co-pulverized; or (3) a method in which a halogen-containing titanium compound and an electron-donating compound are co-pulverized. There is a method of co-pulverizing the pulverized material and a magnesium compound to react with each other. The amount of the electron donating compound to be used is preferably 0.05 to 1 mole of the magnesium compound.
It is 10 mol, more preferably 0.01 to 1 mol.

Furthermore, in the methods (2) and (3), it is not preferable to use a large amount of titanium compound, and it is usually 0.0000% relative to the magnesium compound. The amount of O used is preferably about 1 to 1 mol.

As an example of reaction conditions, a rotary ball mill made of stainless steel (8U832) with an internal volume of 800111A! ,
When 100 balls made of stainless steel (8U832) with a diameter of 15mm are housed in a ball mill cylinder with an inner diameter of 100yx, and the amount of workpiece to be processed is 20 to 40 balls, the number of revolutions is 1.
25 r, p, m, for preferably 24 hours or more, more preferably 48 hours or more. The temperature is usually room temperature to about 100°C.

On the other hand, the slurry method when using an electron-donating compound is
A product obtained by reacting a magnesium compound and an electron-donating compound in an inert solvent or by dissolving or suspending a magnesium compound in a liquid electron-donating compound and a halogen-containing titanium compound in an inert solvent. This is a method in which the reaction is carried out by means such as suspension or co-pulverization. Here, the amount of electron donating compound used is magnesium compound 1
It is preferably 0.01 to 10 mol, more preferably 0.05 to 6 mol. The reaction takes place at room temperature to 200 ℃
This is carried out at ℃ for about 5 minutes to 5 hours.

In addition, some manufacturing examples include:
Publication No. 2, JP-A-54-41985, JP-A-54
-41985 publication 9% Kaisho 55-729 publication, /l
? Publication No. 55-13709, Japanese Patent Publication No. 57-1200
Publication No. 6, JP-A-57-141409, JP-A-5
The method disclosed in Japanese Patent No. 8-127710 may also be used.

The catalyst component thus obtained containing at least titanium, magnesium and... is used in the present invention.

In the present invention, in order to produce a copolymer grafted with an olefin, an organoaluminum compound is first added to an olefinic polymer having an oxygen-containing functional group and a vinyl group. Here, the method of adding the organoaluminum compound is not particularly limited, and any method may be used as long as the two compounds can be brought into sufficient contact with each other. Usually, a suitable method is to add an organoaluminum compound to an olein-based polymer having an oxygen-containing functional group and a vinyl group in a suitable solvent, and stir the mixture at room temperature to 40"C for 5 to 10 minutes. The solvent used is propane,
Preferred are those which can be used as polymerization solvents, such as saturated aliphatic hydrocarbons such as butane, isobutane, hexane, and heptane, and alicyclic hydrocarbons such as cyclopentane and cyclohexane.

The amount of the organoaluminum compound used is a so-called catalytic amount.

In particular, when the organoaluminum compound is a compound having an alkyl group, the ratio of the oxygen-containing functional group in the olefinic polymer having an oxygen-containing functional group and a vinyl group to the alkinothymole ratio in the organoaluminum compound is preferably 1 or less. is used in an amount of 0.5 to 0.8. It should be noted that if the amount of the organoaluminum compound used is too small, the polymerization activity will decrease, which is not preferable.

In the method of the present invention, as described above, an organoaluminum compound is added to an olefinic polymer having an oxygen-containing functional group and a vinyl group, and then the catalyst component, that is, a catalyst component containing at least titanium, magnesium, and a norogen, and an olefin are added. A graft copolymerization reaction is carried out. The catalyst component and the olefin may be added in any order, and may be added at the same time. Furthermore, during copolymerization, in addition to the catalyst component and olefin, the above-mentioned electron-donating compound may be added. In this case, it is effective for polymerizing α-olefins having 3 or more carbon atoms. Here, the amount of olefin to be used varies depending on the physical properties of the intended graft copolymer and cannot be unambiguously determined. When the amount of olefin used is significantly excessive with respect to the olefinic polymer having oxygen-containing functional groups and vinyl groups, the resulting graft copolymer is a mixture of a copolymer with a large graft chain and an olefin homopolymer. However, even such a material may be used as long as it has excellent adhesiveness, dyeability, etc.

On the other hand, the amount of the catalyst component containing at least titanium, magnesium, and halogen is sufficient to be a so-called catalytic amount. Specifically, as a titanium atom, o, o o i~5
Millimoles/! , preferably 0.005 to 1 mmol/!
It is.

The reaction conditions for the graft copolymerization reaction of the present invention vary depending on the catalyst used, raw materials, etc., and cannot be unambiguously determined, but are usually at a temperature of 30 to 250°C, preferably 60 to 90°C, and a pressure of normal pressure to 50°C. 9/α2G for io minutes to 10 hours.

As described above, in the method of the present invention, an organoaluminum is first added to an olefinic polymer having an oxygen-containing functional group and a vinyl group, and then a catalyst component containing a small amount of motitanium, magnesium, and rogene and an olefin are added. It is necessary to add. Even if these compounds and catalyst components are added at the same time or added in an order other than the above and allowed to react, the desired graft copolymer cannot be obtained.

By carrying out the reaction in the above order, the catalyst activity is extremely high and the graft copolymerization anti-catalyst activity is high, so only a small amount of catalyst is needed, and as a result, it is necessary to perform deashing treatment after the copolymerization reaction is completed. The manufacturing efficiency is extremely high. In addition, the graph) polymer obtained by the method of the present invention has excellent adhesive properties, dyeability, etc., and is extremely useful as a raw material for products that require these physical properties.

Next, the present invention will be explained with reference to Examples. Note that all operations in the following Examples and Comparative Examples were performed under an argon stream. Further, the catalytic activity achieved in Examples and Comparative Examples was defined as follows.

Catalyst activity Weight (kg) of total polymer produced per titanium atom in polymerization under conditions of -80°C, 1 hour, ethylene partial pressure 51 Image 2.

Example 1 (1) Preparation of catalyst components In a 500 #I/4-eye flask, 159 sJ of dehydrated purified n-hebutane, jetoxymagnesium io, oy (
88 mmol) and 2.64 g (1
7.6 mmol) was added thereto, and the reaction was carried out under reflux for 1 hour. Then, 83 g (440 mmol) of titanium tetrachloride was added dropwise at 70° C. over 30 minutes, and the reaction was carried out under reflux for 3 hours. Next, the supernatant liquid was extracted by decanting at 80° C. and washed twice with 250 d of n-heptane. Furthermore, 150-h of n-heptane was added, the temperature was raised to 70°C, 83 g (440 mmol) of titanium tetrachloride was added dropwise over 30 minutes, the reaction was carried out under reflux for 3 hours, the supernatant was extracted, and the n-heptane 250d was added for washing. The obtained solid component was washed repeatedly until free titanium tetrachloride was no longer detected to obtain a solid catalyst component. As a result of measuring the amount of titanium supported on the obtained catalyst component by colorimetric method,
2 erq-Tl/g-carrier.

(2) Production of ethylene graft copolymer n-hebutane 400517 dehydrated and purified in an autoclave.
Liquid polybutadiene rubber (1,2-vinyl foundation 1120) which has hydroxyl groups at both ends of the molecule as an olefin polymer
%, number average molecular weight 3000), 12 mmol of triethylaluminum and 0.02 mmol of titanium as the catalyst component obtained in (1) above were sequentially added in this order, and the temperature was raised to 80 °C. Next, hydrogen was introduced into the reactor at 3 kst/cm"G, and then ethylene was introduced continuously to maintain the total pressure at 8.5 kg/an"G, and a graft polymerization reaction was carried out for 1 hour. After the reaction was completed, unreacted gas was purged and unreacted liquid polybutadiene rubber was removed by heating to obtain 58.89 g of a graft copolymer. The content of polybutadiene rubber was determined from the infrared absorption spectrum.The results are shown in Table 1.

Example 2 In Example 1 (2), liquid polybutadiene (1,
2-vinyl group content 20%, number average molecular weight 1000) 10
EXAMPLE 1 (2) I+Open Smoked VI Ii Reso I U7 Kitaju Fuku was prepared except that 9 and 26 mmol of triethylaluminum were used. The results are shown in Table 1.

Example 3 In Example 1 (2), liquid polybutadiene rubber (having hydroxyl groups at both ends of the molecule) was used as the olefin polymer.
1,2-vinyl group content 90%, number average molecular weight 3000)
An ethylene graft copolymer was produced in the same manner as in Example 1 (2) except that 10 g of triethylaluminum was used and 14 mmol of triethylaluminum was used. The results are shown in Table 1.

Practical Hakama Example 4 In Example 1 (2), the olefin polymer was a liquid polypucdiene rubber (1,2-vinyl base i90%) having carboxyl groups at both ends of the molecule.

An ethylene graft copolymer was produced in the same manner as in Example 1 (2), except that a number average molecular weight of 1000) was used, 9 mmol of triethylaluminum, and 9 mmol of diethylaluminum chloride. The results are shown in Table 1.

Comparative Example 1 In Example 1 (2), the addition order to the autoclave was changed to 12 mmol of triethylaluminum, 12 mmol of triethylaluminum, Example 1 (l
A graft copolymer was produced in the same manner as in Example 1 (2), except that 0.02 mmol of the catalyst component obtained in ) was added in the form of titanium and 10 moles of liquid polybutadiene rubber. The results are shown in Table 1.

Examples 5 to 7 Ethylene graft copolymers were produced in the same manner as in Example 1 (2) except that the reaction temperature during graft polymerization was set to the temperature shown in Table 1. . The results are shown in Table 1.

Examples 8 to 9 400 d of a solvent mainly composed of dehydrated and purified dodecane, 10 ml of liquid polybutadiene (same as in Example 1), and 12 mmol of triethylaluminum were added to a single autoclave, and the temperature was raised to the temperature shown in Table 1. Then, 8 mmol of diethylaluminum chloride and O,OS mmol of the catalyst component obtained in Example 1 (2) as titanium were added. Next, 3 kg/c♂G of hydrogen was introduced, and then ethylene was continuously reacted. After the reaction was completed, unreacted gas was purged, and unreacted liquid polybutadiene rubber was removed by thermal filtration to obtain an ethylene graft copolymer. The results are shown in Table 1.

Example 10 (Preparation of catalyst components) In a 500 #lj four-eye flask, 150 aff of dehydrated n-heptane, dichloromagnesium was dissolved in excess ethanol, and dichloromagnesium.6 obtained by distilling off the ethanol. Ethanol A/(Mg01.・60111
! 1111011 ) 10.02 (26,9 mm A
) and 0.819 (5.4 mmol) of ethyl benzoate were added, and the reaction was carried out under reflux for 1 hour. Next, the temperature was raised to 70"C, and titanium tetrachloride (519C, 269 mmol) was added dropwise over 30 minutes, and the reaction was carried out under reflux for 3 hours. After the reaction was completed, washing was repeated using ■-hebutane to remove the catalyst components. The amount of titanium supported was 15 da-T.
i/g-carrier.

(2) Production example 1 (2) of ethylene graft copolymer
An ethylene graft copolymer was produced in the same manner as in Example 1 (2) except that the catalyst component obtained in (1) above was used as the catalyst component. The results are shown in Table 1.

Example 11 (11 Preparation of catalyst components) In a 500 mJ four-eye flask, dichloromagnesium was dissolved in dehydrated WIL n-hebutane 150'ILt, excess ethanol, and dichloromagnesium obtained by distilling off the ethanol. 6 ethanol (Mg0j, ・60, H,
OH) 10.09 (26.9 mmol) and titanium tetrachloride 25.59 (134.5 mmol) were added dropwise, and the reaction was further carried out under reflux for 3 hours. After the reaction was completed, washing was repeated using n-hebutane until free titanium tetrachloride disappeared to obtain a solid catalyst component. The amount of titanium supported is 9
s1R9-ri/g-carrier.

Preparation Example 1 of +21 ethylene graft copolymer (2
), Example 1 (2) was followed except that the catalyst component obtained in (υ) above was used as the catalyst component.
Shown in the table.

40 dehydrated and purified n-hebutane in an autoclave of 11
01R1, liquid polybutadiene rubber (1,2-vinyl group content 20%, WX average molecular weight 3000) having hydroxyl groups at both ends of the molecule as an olefin polymer was added, and triethylaluminum, methyl p-toluate, and Using the catalyst component obtained in Example 1 (1) or Example 10 (1) as titanium, 0.02 mmol was sequentially added in this order, and 0.8 ky/cm" of propylene was added at room temperature.
G, and prepolymerization was carried out for 15 minutes. Next, the temperature was raised to 70°C, and hydrogen was added at a rate of 0.3 kg/cm".
After introducing propylene so that the total pressure was 8 kf/cm2.G, a graft copolymerization reaction was carried out for 2 hours while maintaining the total pressure of 8 kf/cm2.G. After the reaction was completed, unreacted gas was purged, and unreacted liquid polybutadiene rubber was removed by thermal filtration to obtain a graft copolymer. The content of liquid polybutadiene rubber in this graft copolymer was determined from an infrared absorption spectrum. The results are shown in Table 2.

Claims (6)

[Claims] (1) In producing an olefin-grafted copolymer, an organic alumina compound is added to an olefinic polymer having an oxygen-containing functional group and a vinyl group, and then a catalyst component containing at least titanium, magnesium, and halogen is added. A method for producing a graft copolymer, which comprises adding and reacting an olefin. (2) The organoaluminum compound has the general formula IiL', Al
(In the formula, R1 represents an alkyl group, a cycloalkyl group, or an aryl group.) or the general formula 18A! Compounds represented by the general formula R", A7X" (
In the formula, X1 represents a halogen atom, and R1 is the same as above. )
Claim 1, which is a mixture of compounds represented by
Manufacturing method described in section. (3) The ratio (mole ratio) of the oxygen-containing functional group of the olefin polymer to the alkyl group of the organoaluminum compound is 1
The manufacturing method according to claim 1, which is as follows. (4) The production method according to claim 1, wherein the oxygen-containing functional group of the olefin polymer is a hydroxyl group or a carboxyl group. (5) Claim 1 in which the olefin is ethylene
Manufacturing method described in section. (6) The manufacturing method according to claim 1, wherein the olefin is propylene.