JPH0445105A - Olefinic polymer having both modified terminals and its production - Google Patents

Abstract

PURPOSE:To obtain the subject polymer for macromonomers, etc., by reacting ethylene, etc., in the presence of a reaction product of a catalyst composed of a V chelate compound and a dialkylaluminum halide with an alpha,omega-diolefinic compound, and then reacting the resultant product with a proton donor. CONSTITUTION:The objective olefinic polymer is obtained by polymerizing ethylene or propylene in the presence of a reaction product of a polymerization catalyst composed of a vanadium chelate compound and a dialkylaluminum halide expressed by the formula R<1>2AlX (R<1> is 1-20C alkyl ; X is halogen) with an alpha,omega-diolefinic compound expressed by formula I ((m) is 1-15), reacting the resultant polymer with the diolefinic compound and then with a proton donor. The aforementioned olefinic polymer is composed of recurring units expressed by formula II (R is H or methyl) and groups H2C=CH are linked to both terminals thereof. The number-average molecular weight of the polymer is 300-500,000.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an ethylene or propylene polymer having vinyl groups at both ends and a method for producing the same.

2. Description of the Related Art A method is known in which propylene is polymerized using a polymerization catalyst consisting of a vanadium chelate compound and a dialkyl aluminum halide, and the terminals of the resulting polypropylene are modified with a functional group. However, conventional methods allow modification of only one end of the polymer.

Problems to be Solved by the Invention If functional groups can be introduced at both ends of olefin polymers such as ethylene and propylene, a wide range of applications such as macromonomers for polycondensation can be expected.

An object of the present invention is to provide an olefin polymer having vinyl groups introduced at both ends, which is a precursor of an olefin polymer having oxy groups or substituents thereof introduced at both ends.

Means for Solving the Problem The present inventors conducted extensive research and found that α,ω-diolefin compounds can be produced before and after polymerizing ethylene or propylene using a polymerization catalyst consisting of a vanadium chelate compound and a dialkyl aluminum halide. The present invention was completed based on the discovery that an olefin polymer having vinyl groups at both ends could be synthesized by reacting with .

Summary of the invention That is, the summary of the present invention is (1) an olefin polymer having a number average molecular weight of 300 to 500,000, consisting of repeating units of -fcH2.CHR, and having 12c=cH- groups bonded to both ends thereof. , [However, R represents a hydrogen atom or a methyl group. ] (2)
Vanadium chelate compound and general formula l112^IX [However, R1 is an alkyl group having 1 to 20 carbon atoms, and χ represents a halogen atom. ] and a polymerization catalyst consisting of a dialkyl aluminum halide of the general formula H2C=CH→C-L-10-
CLCL C However, m is 1-15. 〕〕α,
The olefin polymer according to (1) above, which comprises polymerizing ethylene or propylene in the presence of a reactant with an ω-diolefin compound, then reacting with the diolefin compound, and then reacting with a proton donor. The manufacturing method is in .

Olefin polymer The olefin polymer of the present invention is represented as described above, and R
is an ethylene polymer in which R is a hydrogen atom, or a propylene polymer in which R is a methyl group.

The olefin polymer of the present invention has a molecular weight of 300 to 500,000
The number average molecular weight (In) is preferably 500 to
It has three units worth 200,000.

Method for producing olefin polymer (1) Reaction of polymerization catalyst and diolefin compound The polymerization catalyst consists of a vanadium chelate compound and dialkyl aluminum halide.

The vanadium chelate compound has the following general formula. In this general formula, R2-R4 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. However, at least one of R2-R4 must be a hydrogen atom, but R2-R4
must not all be hydrogen atoms.

Specific examples included in the above formula will be explained below.

- When R3 is a hydrogen atom and R2 and R4 are hydrocarbon groups.

R2/R': CH3/C6*, CH3/C2H
's, C2H%/C2H,.

CH3/C6s, CH3/CaH-, C6H5/C
a) Is.

CHa/C5HsCL, C, 8% [:82/C,R
5CH2.

CzHs/CaHsCL, CJs/C5HsCH2
- When R3 is a hydrocarbon atom, one of R2 and R4 is a hydrogen atom, and the other is a hydrocarbon atom.

R3/R" or R': C) 1./CH,, C2H
5/CH,.

CH3/[:2L, C2H,/C2H5, C, H5
/CH,.

CH3/C6)Is, Ca)Is/Cz)R6,C
2H5/C-R5.

CH3/CgHs, C, H, CH, /CH,.

CH3/C6H5CH2, C5H5CH2/CaH3 [
l:R2.

C6H5CH2/C2)1s, C2H5/C6H5
CH2.

C6H5CH2/C3H5, C, H, /C, H3CLR
When 3 is a hydrogen atom, one of R2 and R4 is a hydrogen atom, and the other is a hydrocarbon atom.

R2 or R': C)1. , C2)15.
CgH,,C,)l,['H.

Among these, the following compounds are particularly desirable.

■ (acetylacetate Tonato) V (1,3-butanedionato).

The dialkyl aluminum halide is represented by the above general formula, and specific examples thereof include dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, and the like.

The usage ratio of vanadium chelate compound and dialkyl aluminum halide is per mole of the vanadium compound,
The dialkyl aluminum halide is 1 to 1,000 moles.

α,ω-Diolefin compounds have the general formula % formula % It is 15. ).

Specific examples of the diolefin compound include 1°4-pentadiene, 1,5-hexadiene, 1°6-heptadiene, 1,7-octadiene, 1°8-nonadiene, 1.
9-Te°Casien, 1. l〇-Undecadiene, 1.1
1-dodecadiene, 1゜13-tetradecadiene, 1,
Examples include 15-hexadecadiene and 1.17-octadecadiene.

The reaction between the polymerization catalyst and the diolefin compound is preferably carried out in a solvent that is inert and liquid during the reaction, and examples of such solvents include propane, butane, pentane, hexane, heptane, toluene, etc. Examples include hydrocarbons.

The reaction is carried out at -50°C or lower, preferably -65°C or lower for 1 minute to 10 hours, preferably 5 minutes to 2 hours.

The reaction ratio between the polymerization catalyst and the diolefin compound is 0.0 to 10 moles, preferably 0.5 to 2.0 moles, of the vanadium compound in the polymerization catalyst per 1 mole of the diolefin compound.
It is 0 mole.

(2) Polymerization of olefins Polymerization of ethylene or propylene is preferably carried out by supplying ethylene or propylene to the reaction system of (1) above in the presence of the reaction product obtained in (1) above, and The reaction is carried out in the same temperature range as in case (1) above, and for a longer time than in case (1) above. Especially the reaction temperature is -6
When the temperature is below 5°C, a nearly monodisperse polymer with a weight average molecular weight/'IO (number average molecular weight) of -1.05 to 1.5 can be obtained. rate and molecular weight can be increased.

(3) Reaction with diolefin compound The reaction between the reaction product in (2) above and the diolefin compound is preferably carried out by introducing the diolefin compound into the reaction system in (2) above, The reaction conditions are as described in (1) above.
The same is true for .

(4) Reaction with a proton donor Water, alcohol, inorganic acid, etc. can be used as the proton donor. Examples of the alcohol include methanol, ethanol, propatool, etc., and examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, etc. The purpose of using a proton donor is to act on the terminal end of the polymer to remove the polymerization catalyst and donate protons to precipitate the polymer.

The reaction with the proton donor is -100°C to 1200°C,
Preferably, the reaction is carried out at 0 to 150°C for 1 minute to 10 hours, preferably 0.1 to 2 hours. The proton donor is usually used in large excess.

In this way, the olefin polymer of the present invention can be produced, but since the above production method is adopted, the polymer has a structure of the diolefin compound skeleton and the dialkyl aluminum halide used during production. It is presumed that the following microstructure containing the alkyl group R1 is adopted.

^-Lid-CH,・CHR→7B However, 8 and B are as follows, It is an integer that corresponds to the average molecular weight.

n is a number H, C-CH- C, H2゜LC=CH -CH-(CL→coR1 C-J2 (m-LI LCL or the olefin polymer of the present invention is then reacted with diborane and then , by reacting with alkali hydroxide and hydrogen peroxide, both ends are oxidized (-CH2-CH,DH)
It can be made into a polymer.

Reacting the olefin polymer of the present invention with sulfuric acid and water,
Oxygen groups were introduced into the β-positions of both ends (-CH-CH,)
Sodium boron hydride (Na
By reacting with BH4), both terminal leaves can be obtained.

Furthermore, the polymer oxidized as described above is prepared by the general formula R5aS+Y [where R is a hydrocarbon group having 1 to 5 carbon atoms and Y is a halogen atom]. [C) 12-CH20SIR53 or -CH(O3IR
53) CH2F or general formula R'CDDH [However, R6 represents an alkyl group having 1 to 5 carbon atoms. ] by reacting with carboxylic acid.

The oxidation, silyloxylation and esterification reactions will be explained below.

(5) Reaction with diborane The reaction between the olefin polymer of the present invention and diborane is usually carried out preferably in the presence of a solvent such as ether, and
It is carried out at 0° C. for 1 minute to 10 hours. The ether preferably has a boiling point of 100 DEG C. or higher, and aliphatic ethers such as di-n-butyl ether, di-S-butyl ether, diroamyl ether, and di-1-amyl ether are particularly preferable.

Diborane is usually used as a solution in tetrahydrofuran, and the amount used is 0.2 to 1 mole of the diolefin compound used in (1) and (3) above.
The amount is 100 mol, preferably 0.5 to 20 mol.

(6) Reaction with alkali hydroxide and hydrogen peroxide The reaction with alkali hydroxide and hydrogen peroxide is carried out at 0 to 100°C for 1 hour to 1 week.

As the alkali hydroxide, sodium hydroxide and potassium hydroxide are generally used, and their aqueous solutions are usually used. Further, an aqueous solution of hydrogen peroxide is usually used.

The amount of alkali hydroxide and hydrogen peroxide used is as described in (5) above.
It is sufficient if the amount is equal to or more than the diborane used in the above, but it is usually used in large excess.

(By doing so, the olefin polymer of the present invention in which both terminals are hydroxylated can be obtained.

(7) Reaction with sulfuric acid and water The reaction between the polymer of the present invention and sulfuric acid and water is usually carried out at 80 to 150°C for 1 minute to 10 hours in the presence of water or a mixture of water and ether.

(8) Reaction with mercury acetate and water The reaction between the polymer of the present invention and mercury acetate and water is usually carried out at 80 to 150°C for 1 minute to 1 minute in the presence of a mixture of water and ether.
It will be held for 10 hours.

(9) Reaction with sodium boron hydride The reaction of the product obtained in the above (8) with sodium boron hydride may be the same as the reaction method in the above (8).

Reaction with a silane compound or carboxylic acid The silane compound used is represented by the general formula R'5SiY. In the formula, Rs is a hydrocarbon group having 1 to 5 carbon atoms,
Methyl and ethyl are particularly preferred. Further, Y is a halogen atom, and examples thereof include chlorine, bromine, fluorine, and iodine.

Carboxylic acids are represented by the general formula R″COOH.

In the formula, R6 is a hydrocarbon group having 1 to 5 carbon atoms, and methyl and ethyl are particularly preferred.

The reaction of the dioxypolyolefin obtained in the above (6), (7) or (9) with a silane compound or carboxylic acid may be the same as the method generally carried out when trialkylsilylating or esterifying an alcohol.

For example, the reaction with a silane compound typically desirably
In the presence of a solvent such as an amine compound, 1
After reacting both for minutes to 5 hours, an additional 100 to 150
The reaction is carried out by reacting at a temperature of 1 to 10 hours. The most suitable amine compound is one having a boiling point of 100° C. or higher, such as pyridine.

Further, in the esterification reaction, in addition to using the carboxylic acid alone, a small amount of concentrated sulfuric acid or dry hydrogen chloride may be used at the same time. Furthermore, a halide of carboxylic acid can be used instead of carboxylic acid.

The amount of the silane compound or carboxylic acid used should be at least twice the mole of the olefin polymer having oxy groups at both ends.

Effects of the Invention By employing the method of the present invention, it is possible to produce an olefin polymer whose both ends are modified with vinyl groups, and from such a polymer of the present invention, both ends are modified with oxy groups. Or, an olefin polymer modified with the substituent can be easily produced.

In addition, such olefin polymers modified with oxy groups can be widely used as macromonomers for polycondensation.

Example Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 Toluene 1 was added to 31 flasks which were sufficiently purged with nitrogen gas.
．． 01 was added and cooled to -65°C. At the same temperature, 1.2 mmol of 1.7-octadiene was added. Then 10 mmol of AI ((:28S) 2CI and 1 mmol of V(
2-methyl-1,3-butanedionato) 3 and
Stirred for 0 minutes. A further 4.5 g of ethylene were introduced over a period of 2 hours, followed by the addition of 1.2 mmol of 1.7-octadiene.

After stirring for 10 minutes, the reaction solution was poured into ethanol and the produced polymer was filtered. The number average molecular weight (Ayu) of the polymer determined by GPC was 4.9 x 103. Moreover, the yield was 4.3g.

As a result of measuring the buton NMR of the above polymer, the result was 5.0
Terminal double bond (7) 7'o to ppm and 5.8 pptn
) was observed. Their attributions are as follows.

δ (ppm) Attribution δ (ppm) Attribution 5, 0 -CH=C]2 5.8 -[
:) l=cH.

This signal and 1,3 pp due to ethylene polymer
From the intensity ratio of the peaks of m, l1ln was determined to be 4.6X103 assuming that vinyl groups were present at both ends.

This value agrees well with the result obtained by GPC.

It was concluded that the obtained polymer was an ethylene polymer having vinyl groups at both ends.

The above polymer was added to 200W11 n-butyl ether, and a THF solution of diborane was added at room temperature while stirring vigorously under nitrogen flow. The amount of borane added was 2.5 mmol. After stirring at reflux temperature for 1 hour, the temperature was lowered and 200ml of 3N aqueous sodium hydroxide solution was added.
1 and 200 d of 30% hydrogen peroxide solution were added, and the mixture was further stirred for 1 day. The resulting polymer was washed thoroughly with water, then with acetone, and then dried.

The IR (infrared absorption spectrum) chart of the produced polymer had a broad peak at 3300 to 3500 cm-'. This shows that it contains an oxy group.

The above ethylene polymer and 10g of trimethylchlorosilane were added to 200g of pyridine, stirred at 25°C for 1 hour, and then
Refluxed for an hour. The produced polymer was washed with methanol and dried. The result of proton NMR measurement was 0.08 ppm.
A signal due to the proton of the St (CH,I) s group was observed. From the intensity ratio of this signal and the peak at 1.3 ppm caused by the ethylene polymer, Mn=5.
It was found to be 5X10'. This value agrees well with the value determined by GPC.

From this, it was concluded that an ethylene polymer having trimethylsilyloxy groups at both ends was synthesized.

Furthermore, as a result of IR analysis, this ethylene polymer with trimethylsilyloxy groups at both ends has a COI of 3300 to 3500.
-' peak was not observed.

Therefore, it can be concluded that the polymer before reacting with trimethylchlorosilane is an ethylene polymer having oxy groups at both ends.

Example 2 Toluene 1 was added to 31 flasks which were sufficiently purged with nitrogen gas.
．． 01 was added and cooled to -78°C. At the same temperature, 0.6 mmol of 1.9-decadiene was added. Next, 100 mmol of ^l (C2H5) 2CI and 20 mmol of (acetylacetonate) were added and stirred for 30 minutes. After introducing an additional 1.5 g of ethylene over 30 minutes, 1.9-decadiene was added to 0.6 m! J mol was added.

After stirring for 30 minutes, the reaction solution was poured into ethanol and the produced polymer was filtered. Yield was 1.2g.

Next, except that the amount of diborane used was 1 mmol,
An oxidation reaction was carried out in the same manner as in Example 1. IR analysis of the produced polymer revealed that it was 3300 to 3500 cm-'
A broad peak was observed.

The three points of the oxidized polymer measured by GPC are 2 and 6.
x 10'.

Example 3 The ethylene polymer of the present invention was grown in the same manner as in Example 1, except that 1.5 g of ethylene was introduced over 30 minutes. The l1ln of the polymer determined by proton NMR is 1.5
It was x 103.

Example 4 Toluene 1 was added to 31 flasks which were sufficiently purged with nitrogen gas.
．． 07 was added and cooled to -78°C. At the same temperature, 1.5 mmol of 1.7-octadiene was added. Next, 100 mmol of ^1 (C2H5) 2C1 and 20 mmol of ■(
acetylacetonate) 3 was added and stirred for 30 minutes. 3
5 g of propylene was added and polymerization was carried out for 1 hour. Add another 3.0 mmol of 1,7-octadiene,
After stirring for 0 minutes, the reaction solution was poured into ethanol, and the produced polymer was filtered off. Yield was 6.1g.

As a result of proton NMR measurement of the above polymer, 5.0
Signals based on terminal double junction protons were observed at ppm and 5.8 ppm.

0,7-1 due to this signal and propylene polymer.
．． From the intensity ratio of the peak at 7 ppm, the value of l1ln calculated assuming that vinyl groups exist at both ends is 5.1 x 1
It was 03.

When this polymer was analyzed by GPC, Ii%n was 6,
OX 10''. From this, it was concluded that the obtained polymer was a propylene polymer having vinyl groups at both ends.

Next, add 500all! of this polymer! dissolved in THF of
A solution of diborane in THF was added at room temperature with vigorous stirring under nitrogen flow. The amount of diborane added was 3 mmol. After stirring at room temperature for 4 hours, 3N sodium hydroxide aqueous solution and 30% hydrogen peroxide solution were added, and the mixture was further stirred for 1 day. The resulting polymer was thoroughly washed with water, then with acetone, and then dried.

When the IR of the produced polymer was measured, it was 3300 to 350.
A broad peak due to the oxy group was observed at 0 cm-'.

The number average molecular weight measured by GPC was 4.8 x 103. A reaction with trimethylchlorosilane was carried out in the same manner as in Example 1. Proton NMR of the produced polymer shows 0.
A peak due to hydrogen of the trimethylsilyl group was observed at 0.08 ppm, and a peak due to protons of the propylene polymer was observed at 0.7 to 1.7 ppm. From the intensity ratio of both peaks, it was determined that Ayu = 5.6 x 10'.

Claims (1)

[Claims] (1) An olefin polymer with a number average molecular weight of 300 to 500,000, consisting of the repeating unit of ▲, which has mathematical formulas, chemical formulas, tables, etc., and H_2C=CH- groups bonded to both ends. [However, R represents a hydrogen atom or a methyl group. ] (2) Vanadium chelate compound and general formula R^1_2AlX [However, R^1 represents an alkyl group having 1 to 20 carbon atoms, and X represents a halogen atom. ] Polymerization catalyst consisting of dialkyl aluminum halide and general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, m is 1 to 15. Claim (1), comprising polymerizing ethylene or propylene in the presence of a reactant with an α,ω-diolefin compound, and then reacting with the diolefin compound and then reacting with a proton donor. A method for producing the described olefin polymer.