JP2862336B2 - Both-terminal-modified olefin polymer and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polymer of ethylene or propylene having vinyl groups at both ends and a method for producing the same.

2. Description of the Related Art There is known a method for polymerizing propylene using a polymerization catalyst comprising a vanadium chelate compound and a dialkylaluminum halide, and modifying the terminal of the obtained polypropylene with a functional group. However, in the conventional method,
Only one of the polymer ends can be modified.

Problems to be Solved by the Invention If functional groups can be introduced into both terminals of a polymer of an olefin such as ethylene or propylene, a wide range of applications can be expected in applications such as polycondensation macromonomers.

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

Means for Solving the Problems The present inventors have conducted intensive studies and as a result, before and after polymerizing ethylene or propylene using a polymerization catalyst comprising a vanadium chelate compound and a dialkylaluminum halide, an α, ω-diolefin compound and The inventors have found that an olefin polymer having vinyl groups at both terminals can be synthesized by the reaction, and completed the present invention.

SUMMARY OF THE INVENTION That is, the gist of the present invention is (1) a number average molecular weight of 300 to 500, which is composed of a repeating unit of CH ₂ · CHR, and has H ₂ C CCH— groups bonded to both ends thereof.
000 olefin polymer, wherein R represents a hydrogen atom or a methyl group. ] (2) a vanadium chelate compound of the general formula R ¹ ₂ AIX [where, R ¹ is 1 to 20 alkyl group carbon atoms, X is a halogen atom. A polymerization catalyst consisting of dialkylaluminum halide], the general formula _{H 2 C = CHC m H 2m} CH = CH 2 [where, m is 1 to 15. (1) wherein ethylene or propylene is polymerized in the presence of a reactant with an α, ω-diolefin compound, and then reacted with the diolefin compound and then reacted with a proton donor. The method for producing an olefin polymer of the above.

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

The olefin polymer of the present invention has a number average molecular weight (n) of 300 to 500,000, but preferably has an n of 500 to 200,000.

Production method of olefin polymer (1) Reaction of polymerization catalyst with diolefin compound The polymerization catalyst comprises a vanadium chelate compound and a dialkylaluminum halide.

The vanadium chelate compound has the following general formula.

General formula In this general formula, R ^{2 to} R ⁴ represent a hydrogen atom or carbon atom 1
Represents up to 8 hydrocarbon groups. However, at least one of R ^{2 to} R ⁴ must be a hydrogen atom, but all of R ^{2 to} R ⁴ must not be hydrogen atoms.

 Specific examples included in the above equation will be described below.

-When R ³ is a hydrogen atom and R ² and R ⁴ are hydrocarbon groups.

_{^{R 2 / R 4: CH 3}} / CH 3, CH 3 / C 2 H 5, C 2 H 5 / C 2 H 5, CH 3 / C 6 H 5, C 2 H 5 / C 6 H 5, C 6 _{H 5 / C 6 H 5,} CH 3 / C 6 H 5 CH 2, C 6 H 5 CH 2 / C 6 H 5 CH 2, C 2 H 5 / C 6 H 5 CH 2, C 6 H 5 / C ₆ H ₅ CH ₂ · R ³ is a hydrocarbon atom, and one of R ² and R ⁴ is a hydrogen atom and the other is a hydrocarbon atom.

R ³ / R ² or R ⁴ : CH ₃ / CH ₃ , C ₂ H ₅ / CH ₃ , CH ₃ / C ₂ H ₅ , C ₂ H ₅ / C ₂ H ₅ , C ₆ H ₅ / CH ₃ , CH ₃ / C ₆ H ₅ , C ₆ H ₅
/ C ₂ H ₅ , C ₂ H ₅ / C ₆ H ₅ , C ₆ H ₅ / C ₆ H ₅ , C ₆ H ₅ CH ₂ / CH ₃ , CH ₃ / C ₆ H ₅ CH ₂ , C ₆ H ₅ CH ₂ / C ₆ H ₅ CH ₂ , C ₆ H ₅ CH ₂ / C ₂ H ₅ , C ₂ H ₅ / C ₆ H ₅ CH ₂ , C ₆ H ₅ CH ₂ / C ₆ H ₅ , C ₆ H ₅ / C ₆ H ₅ CH ₂ · R ³ is a hydrogen atom, and one of R ² and R ⁴ is a hydrogen atom and the other is a hydrocarbon atom.

R ² or R ⁴ : CH ₃ , C ₂ H ₅ , C ₆ H ₅ , C ₆ H ₅ CH _2, etc. Among them, the following compounds are particularly desirable.

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

The use ratio of the vanadium chelate compound and the dialkylaluminum halide is 1 to 1,000 mol of the dialkylaluminum halide per 1 mol of the vanadium compound.

The α, ω-diolefin compound has the general formula H ₂ C = CHC _m H
_2m CH = CH ₂ [where m is 1 to 15] ).

Specific examples of the diolefin compound include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene,
7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,13
-Tetradecadiene, 1,15-hexadecadiene, 1,17-
Octadecadienes and the like can be mentioned.

The reaction between the polymerization catalyst and the diolefin compound is preferably carried out in a solvent which is inert in the reaction and which is liquid at the time of the reaction. Examples of the solvent include propane, butane, pentane, hexane, heptane, and toluene. Hydrocarbons and the like.

The reaction is carried out at a temperature of -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 such that the vanadium compound in the polymerization catalyst is 0.0 to 10 mol, preferably 0.5 to 2.0 mol, per 1 mol of the diolefin compound.

(2) Polymerization of olefin In the polymerization of ethylene or propylene, ethylene or propylene is preferably supplied to the reaction system of (1) in the presence of the reaction product obtained in (1), and In the same temperature range as in the case (1), the reaction is carried out for a longer time than in the case (1). The reaction temperature
When the temperature is 65 ° C. or lower, a polymer close to monodispersion of w (weight average molecular weight) / n (number average molecular weight) = 1.05 to 1.5 can be obtained. By increasing the polymerization time, the yield and molecular weight of the polymer can be increased.

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

(4) Reaction with proton donor As the proton donor, water, alcohol, inorganic acid and the like can be used. Examples of the alcohol include methanol, ethanol, and propanol, and examples of the inorganic acid include hydrochloric acid, nitric acid, and sulfuric acid. The use of the proton donor is to act on the terminal of the polymer to release the polymerization catalyst and to donate the proton to precipitate the polymer.

The reaction with the proton donor is carried out at -100 ° C to + 200 ° C, preferably at 0 to 150 ° C for 1 minute to 10 hours, preferably 0.1 to 10 hours.
Performed for 2 hours. The proton donor is usually used in a large excess.

By doing so, the olefin polymer of the present invention can be produced.However, since the polymer adopts the above-mentioned production method, the diolefin compound skeleton and the dialkylaluminum halide used in the production are used. It is presumed to take microstructures as follows including the alkyl group R ¹ therein.

ACH ₂ .CHR _n B where A and B are as follows, and n is an integer corresponding to the number average molecular weight.

The olefin polymer of the present invention is then reacted with diborane and then with alkali hydroxide and hydrogen peroxide to form a polymer having both ends oxylated (-CH ₂ -CH ₂ OH). it can.

The olefin polymer of the present invention was reacted with sulfuric acid and water to introduce an oxy group at the β-position at both ends. Oxy groups were introduced at the β-position of both terminals by reacting with sodium boron hydride (NaBH ₄ ) after reacting with polymer or mercury acetate and water. It can be a polymer.

Further, a polymer obtained by oxylating as described above, the general formula R ⁵ ₃ SiY [where, R represents 1-5 hydrocarbon group having a carbon number, Y
Represents a halogen atom. By reacting a silane compound of the formula [-CH ₂ -C
H ₂ OSiR ⁵ _3, or -CH (OSiR ⁵ ₃₎ -CH _3], or the general formula R ⁶ COOH
[However, R ⁶ represents an alkyl group having 1 to 5 carbon atoms. ), Both ends are esterified Polymer.

Hereinafter, the oxylation, silyloxylation, and esterification reactions will be described.

(5) Reaction with diborane The reaction between the olefin polymer of the present invention and diborane is usually carried out preferably at 100 to 200 ° C. in the presence of a solvent such as ether.
For 1 minute to 10 hours. 100 for ether
Those having a boiling point of not lower than ° C are desirable, and aliphatic ethers such as di-n-butyl ether, di-s-butyl ether, di-n-amyl ether and di-i-amyl ether are particularly desirable.

Diborane is usually used as a solution of tetrahydrofuran, and its use amount is 0.2 to 1 per mole of the total amount of the diolefin compound used in the above (1) and (3).
00 mol, desirably 0.5 to 20 mol.

(6) Reaction with alkali hydroxide and hydrogen peroxide The reaction with alkali hydroxide and hydrogen peroxide is 0 to 100.
C. for one hour to one week.

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

The amounts of the alkali hydroxide and hydrogen peroxide used may be at least equimolar with the diborane used in the above (5), but are usually used in large excess.

Thus, the olefin polymer of the present invention having both ends hydroxylated can be obtained.

(7) Reaction with sulfuric acid and water The reaction of the polymer of the present invention with sulfuric acid and water is usually carried out in the presence of water or a mixture of water and ether at 80 to 150 ° C for 1 minute to 1 minute.
Performed for 0 hours.

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

The reaction between the product obtained in the above (8) and sodium boron hydride may be the same as the reaction method in the above (8).

(10) a silane compound or a reaction silane compounds used in the carboxylic acid is represented by the general formula R ⁵ ₃ SiY. In the formula, R ⁵ is a hydrocarbon group having 1 to ⁵ carbon atoms, and methyl and ethyl are particularly desirable. Y is a halogen atom, such as chlorine, bromine, fluorine and iodine.

Carboxylic acids are represented by the general formula R ⁶ COOH. In the formula, R ⁶ is a hydrocarbon group having 1 to 5 carbon atoms, and methyl and ethyl are particularly preferred.

The reaction between the dioxypolyolefin obtained in the above (6), (7) or (9) and the silane compound or carboxylic acid may be the same as the method generally performed when alcohol is subjected to trialkylsilylation or esterification.

For example, the reaction with a silane compound is usually desirably performed by first reacting both at 0 to 50 ° C. for 1 minute to 5 hours in the presence of a solvent such as an amine compound, and then further at 100 to 150 ° C. It is performed by reacting for 10 hours. As the amine compound, those having a boiling point of 100 ° C. or more, such as pyridine, are optimal.

In the esterification reaction, a small amount of concentrated sulfuric acid or dry hydrogen chloride may be simultaneously used in addition to the carboxylic acid alone. Further, a carboxylic acid halide may be used instead of the carboxylic acid.

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

EFFECT OF THE INVENTION By employing the method of the present invention, it is possible to produce an olefin polymer in which both terminals are modified with a vinyl group. Alternatively, an olefin polymer modified with the substituent can be easily produced.

The olefin polymer modified with such an oxy group can be widely used as a polycondensation macromonomer or the like.

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

Example 1 Toluene 1.
0 l was added and cooled to -65 ° C. At the same temperature, 1.2 mmol of 1,7-octadiene were added. Then 10 mmol Al (C ₂ H ₅ ) ₂
Cl and 1 mmol of V (2-methyl-1,3-butanedionato) ₃ were added and stirred for 30 minutes. Further, after 4.5 g of ethylene was introduced over 2 hours, 1,7-octadiene was added to 1.2 g.
Mmol was added. After stirring for 10 minutes, the reaction solution was poured into ethanol, and the formed polymer was filtered. The number average molecular weight (n) of the polymer determined by GPC was 4.9 × 10 ³ . The yield was 4.3 g.

As a result of measuring the proton NMR of the above polymer, 5.0 ppm and
At 5.8 ppm, a signal based on the proton of the terminal double bond was observed. Their assignments are as follows: than [delta] (ppm) attributable [delta] (ppm) Attribution _{5.0 -CH = C H 2 5.8 -C} H = CH 2 intensity ratio of a peak of 1.3ppm caused by the signal and ethylene polymer, there is a vinyl group at both ends Was 4.6 × 10 ³ .

This value is in good agreement with the result obtained from GPC.
It was concluded that the resulting polymer was an ethylene polymer having vinyl groups at both ends.

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

The IR (infrared absorption spectrum) chart of the produced polymer had a broad peak at 3300 to 3500 cm ^-1 . This indicates that it contains an oxy group.

The above ethylene polymer and 10 g of trimethylchlorosilane were added to 200 ml of pyridine, stirred at 25 ° C. for 1 hour, and then refluxed for 4 hours. The resulting polymer was washed with methanol and dried. Signal caused by -Si (CH _{3) 3} group protons result 0.08ppm proton NMR measurement was observed. From the intensity ratio of this signal and the peak of 1.3 ppm caused by the ethylene polymer, n = 5.5 × 10 ³ was obtained. This value is in good agreement with the value obtained from GPC.

Thus, it was concluded that an ethylene polymer having a trimethylsilyloxy group at both ends was synthesized. In addition, ethylene polymers having trimethylsilyloxy groups at both ends include:
As a result of IR analysis, a peak at 3300 to 3500 cm ^-1 was not observed. Therefore, it can be concluded that the polymer before the reaction with trimethylchlorosilane is an ethylene polymer having both terminal oxy groups.

Example 2 Into a 3 l flask sufficiently purged with nitrogen gas was placed toluene 1.
0 l was added and cooled to -78 ° C. At the same temperature, 0.6 mmol of 1,9-decadiene was added. Then 100 mmol of Al (C ₂ H ₅ ) ₂ C
l and 20 mmol of V (acetylacetonate) ₃ are added,
Stir for 30 minutes. After 1.5 g of ethylene was further introduced over 30 minutes, 0.6 mmol of 1,9-decadiene was added. After stirring for 30 minutes, the reaction solution was poured into ethanol, and the formed polymer was filtered. The yield was 1.2 g.

Next, an oxylation reaction was carried out in the same manner as in Example 1 except that the amount of diborane used was changed to 1 mmol. When the produced polymer was subjected to IR analysis, a broad peak was observed at 3300 to 3500 cm ^-1 .

N of the oxylated polymer measured by GPC is 2.6 × 10 ³
Met.

Example 3 An ethylene polymer of the present invention was produced in the same manner as in Example 1 except that 1.5 g of ethylene was introduced over 30 minutes. The n of the polymer determined by proton NMR was 1.5 × 10 ³ .

Example 4 Into a 3 liter flask sufficiently purged with nitrogen gas was placed toluene 1.
0 l was added and cooled to -78 ° C. At the same temperature, 1.5 mmol of 1,7-octadiene was added. Then 100 mmol of Al (C ₂ H ₅ ) ₂ C
l and 20 mmol of V (acetylacetonate) ₃ are added,
Stir for 30 minutes. 35 g of propylene was added and polymerization was carried out for 1 hour. After further adding 3.0 mmol of 1,7-octadiene and stirring for 30 minutes, the reaction solution was poured into ethanol, and the produced polymer was separated by filtration. The yield was 6.1 g.

As a result of measuring the proton NMR of the above polymer, 5.0 ppm and
At 5.8 ppm, a signal based on the proton at the terminal double junction was observed.

0.7-1.7 due to this signal and propylene polymer
From the intensity ratio of the ppm peak, the value of n obtained assuming that vinyl groups exist at both ends was 5.1 × 10 ³ .

GPC analysis of this polymer showed that n was 6.0 × 10 ³ . From this, it was concluded that the obtained polymer was a propylene polymer having vinyl groups at both ends.

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

When the IR of the produced polymer was measured, a broad peak due to an oxy group was observed at 3300 to 3500 cm ^-1 .

The number average molecular weight measured by GPC was 4.8 × 10 ³ . Reaction with trimethylchlorosilane was carried out in the same manner as in Example 1. The proton NMR of the resulting polymer has a peak at 0.08 ppm due to hydrogen of the trimethylsilyl group,
At 1.7 ppm, a peak due to protons of the propylene polymer was observed. From the intensity ratio of both peaks, n = 5.6 × 1
I got 0 ³ .

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-113001 (JP, A) Japanese Translation of PCT International Publication No. 3-502473 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 8/00-8/50 C08F 2/00 C08F 4/60-4/70 C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00-210/18 C08F 299/00 C08F 290 / 04 CAS ONLINE

Claims (2)

(57) [Claims] 1. A number average molecular weight of 300 consisting of a repeating unit of CH ₂ .CHR and having a H ₂ C ＝ CH— group bonded to both terminals.
~ 500,000 olefin polymers. [However, R represents a hydrogen atom or a methyl group. ] Wherein the vanadium chelate compound of the general formula R ¹ ₂ AIX
Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, and X represents a halogen atom. And a polymerization catalyst comprising a dialkylaluminum halide of the general formula H ₂ C = CHC _m H _2m CH = CH
₂ [where m is 1 to 15. (1) wherein ethylene or propylene is polymerized in the presence of a reactant with an α, ω-diolefin compound, and then reacted with the diolefin compound, followed by reaction with a proton donor. The method for producing the olefin polymer according to the above.