JPH0699514B2 - Method for producing 3-methylbutene-1 polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a 3-methylbutene-1 polymer, more specifically, a stereoregular high-molecular weight 3-methylbutene-1 polymer.

[Conventional technology]

The 3-methylbutene-1 polymer has hitherto been known as a high-melting-point heat-resistant polyolefin, but it has not yet been used as an industrial material.

As one of the causes, it is considered that the 3-methylbutene-1 polymer described in the literature or the like has a low molecular weight, and as a result, the elongation impact strength required as an industrial material was not sufficient. There is.

On the other hand, olefins having a tertiary carbon atom such as 3-methylbutene-1 have low activity when attempting to polymerize with a coordination polymerization catalyst composed of a usual combination of titanium trichloride and an organoaluminum compound, which is industrially difficult. It is also possible that sufficient polymerization activity necessary for production was not obtained.

In the polymerization of propylene, a method of using a catalyst exhibiting a higher activity than that of an ordinary titanium trichloride catalyst is considered, and in Japanese Patent Laid-Open No. 54-107989, the aluminum content is 0.15 or less in terms of the atomic ratio of aluminum to titanium. And a solid titanium trichloride complex catalyst containing a complexing agent is used as a catalyst, and dimethyl n-propyl aluminum monochloride or di-n-hexyl aluminum monochloride as an organoaluminum compound is used as a co-catalyst to polymerize 3-methylbutene-1. In JP-A-57-182305, there is presented a method of using a titanium trichloride-containing solid which does not contain aluminum trichloride at all or contains aluminum trichloride in a molar ratio of 0.1 or less with respect to titanium trichloride. Has been done.

When 3-methylbutene-1 is polymerized by the methods described in these, the polymerization activity is certainly high to some extent as compared with the methods using other catalysts, but it is still insufficient for industrial use. Atsuta

[Object of the Invention]

The inventors of the present invention have conducted extensive studies to solve such problems in 3-methylbutene-1 polymerization. As a result, the solid titanium trichloride complex catalyst used in JP-A-54-107989 and triethyl It has been found that a stereoregular high molecular weight polymer can be obtained with high activity by combining with aluminum, trinormal aluminum or trinormal hexylaluminum, and has reached the present invention. That is, the present invention is obtained by precipitating titanium trichloride liquefied in the presence of ether or thioether at a temperature of 150 ° C. or less, the aluminum content is 0.15 or less in the atomic ratio of aluminum to titanium, and complexing is performed. Using a finely divided solid titanium trichloride complex catalyst containing an agent and triethylaluminum, trinormalpropylaluminum or trinormalhexylaluminum as an organoaluminum cocatalyst, 3-methylbutene-1 is homopolymerized or co-polymerized with other olefins. It exists in the manufacturing method of 3-methylbutene-1 polymer characterized by polymerizing.

[Structure of Invention]

To explain the present invention in more detail, the monomers used for polymerization in the present invention include 3-methylbutene-1 alone and 3
A mixture of methylbutene-1 with another olefin which is copolymerizable.

Other olefins include chain α-olefins having a C _{2 to} C _{15 level of} ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1 and the like. Besides, vinylcyclohexane, styrene, etc. may be mentioned.

The proportion of these olefins in the polymer is at most 30.
It is about 20% by weight, preferably 20% by weight or less. Increasing the copolymerization amount of other olefins beyond this is essentially 3-
Methylbutene-1 polymer is not preferable because it loses characteristics such as high melting point and high rigidity.

Further, the copolymerization method includes not only random copolymerization but also block copolymerization, which is usually called a propylene polymer.

The solid titanium trichloride catalyst complex used as a catalyst in the present invention has an aluminum content of 0.15 or less, preferably 0.1 or less, more preferably 0.02 or less in terms of an aluminum atomic ratio to titanium, and contains a complexing agent. It is a thing. The content of the complexing agent is 0 in terms of the molar ratio of the complexing agent to titanium trichloride in the solid titanium trichloride catalyst complex.
It is 001 or more, preferably 0.01 or more. Specifically, for example, the formula TiCl ₃ · (AlR ¹ nX _3- n) x (C) y (wherein, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and n is Is a number of 0 ≦ n ≦ 2, C is a complexing agent, x is a number of 0.15 or less, and y is a number of 0.001 or more.) Of course, TiCl _{In addition to the three} components, the AlR ¹ nX ₃ -n component and the complexing agent C component, a small amount of iodine, an inert inorganic solid such as MgCl ₂ or MgO, or an olefin polymer powder such as polyethylene or polypropylene is contained. May be. Examples of the complexing agent C include ethers, thioethers, ketones, carboxylic acid esters, amines, carboxylic acid amides, polysiloxanes, etc. Among them, ethers or thioethers are particularly preferable. As an ether or thioether,
Those represented by the general formula R ² —O—R ³ or R ² —S—R ³ (in the formula, R ² and R ³ represent a hydrocarbon group having 15 or less carbon atoms), which will be specifically described later. Something like this. AlR ¹ nX ₃ −
Examples of n include AlCl ₃ and AlR ¹ Cl ₂ .

Further, the solid titanium trichloride catalyst complex used in the method of the present invention has an X-ray diffraction pattern having a maximum intensity halo at the position corresponding to the strongest peak position of α-type titanium trichloride (2θ = 32.9 °). Is particularly preferable. Further, it is preferable that the solid titanium trichloride catalyst complex is not subjected to a heat history at a temperature exceeding 150 ° C. during the production.

However, such a solid titanium trichloride catalyst complex is obtained by a method of precipitating liquefied titanium trichloride in the presence of ether or thioether at a temperature of 150 ° C. or lower.

This method is already used in Japanese Patent Application Nos. 49-88476, 49-88477, and
49-120100, 50-1154, 50-16722, 50-19552,
No. 52-140922, No. 52-147590, etc., but specifically, the following two methods can be mentioned as a method for obtaining liquefied titanium trichloride.

(A) A method in which titanium tetrachloride is used as a starting material, and this is reduced with an organoaluminum compound in the presence of an ether or a thioether and, if necessary, a suitable hydrocarbon solvent.

(B) A method of treating solid titanium trichloride as a starting material with ether or thioether in the presence of a suitable hydrocarbon solvent, if necessary.

Examples of the ether or thioether used include those represented by the general formula shown above.
As R ² and R ³ , ethyl, n-propyl, n-butyl,
Alkyl groups such as n-amyl, n-hexyl, n-heptyl, n-octyl, n-decyl and n-dodecyl, preferably linear alkyl groups; alkenyl groups such as butenyl and octenyl, preferably linear alkenyl. Group; an aryl group such as tolyl, xylyl and ethylphenyl, an aralkyl group such as benzyl and the like. Preferred are dialkyl ethers, dialkenyl ethers, alkylalkenyl ethers, dialkyl thioethers and the like.

As the hydrocarbon solvent, saturated aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-dodecane and liquid paraffin; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, etc., which are appropriately selected mainly depending on the type of ether.
For example, as an ether or thioether, at least one of R ² and R ^{3 in} the general formula shown above is an alkyl group having 3 to 5 carbon atoms,
When an alkenyl group is used, preferably aromatic hydrocarbon is selected, and then alicyclic hydrocarbon is selected.
When using an ether in which R ² and R ³ are an alkyl group or an alkenyl group having 6 or more carbon atoms, a saturated aliphatic hydrocarbon is preferably selected.

Next, as the organoaluminum compound in the method (A), for example, a general formula AlR ⁴ mX ₃ -m (in the formula, R ⁴ has 1 to 2 carbon atoms)
A compound represented by a hydrocarbon group of 0, m is a number of 1 to 3 and X is a halogen atom is used. The amount of the compound is titanium in titanium tetrachloride: hydrocarbon in an organoaluminum compound. The molar ratio with the group (R ^{4 in the} general formula) is in the range of 1: 0.1 to 1:50, preferably 1: 0.3 to 1:10. The amount of ether or thioether used is 1: 0.05 to 1: 5, preferably in the molar ratio of ether: titanium tetrachloride, preferably
It is in the range of 1: 0.25 to 1: 2.5. The reduction reaction is carried out by any method, and usually, the three components are contacted in any order at a temperature of about 0 to 50 ° C. to form a liquid substance.

As the titanium trichloride in the method (B), titanium trichloride produced by reducing titanium tetrachloride with hydrogen gas, aluminum or the like can be used, but it is produced by reducing titanium tetrachloride with an organic aluminum compound. Titanium trichloride is especially preferred. The amount of ether or thioether used is 1: 1 or more in terms of titanium trichloride: ether or thioether molar ratio,
It is preferably 1: 1 to 5. The ether or thioether treatment is usually carried out at a temperature of 0 to 100 ° C, preferably about 20 to 50 ° C.

When finely particulate solid titanium trichloride is precipitated from titanium trichloride liquefied by any of the above methods (A) and (B) at a temperature of 150 ° C or lower, the method is not particularly limited, and the liquid substance as it is or necessary After adding a hydrocarbon diluent depending on the temperature of 150 ℃ or less, usually 20 ~ 150 ℃, preferably 40
The temperature is raised to ˜120 ° C., particularly preferably 60 to 100 ° C. to deposit. When the total number of moles of titanium and aluminum in the liquid titanium trichloride is less than the number of moles of ether or thioether, a liberating agent may be added to promote precipitation. The liberating agent has a function of reacting with a complex of titanium trichloride and ether or thioether constituting the liquid material to precipitate free solid titanium trichloride, and has a stronger acidity than titanium trichloride. Examples thereof include Lewis acids such as titanium tetrachloride, boron trifluoride, boron trichloride, vanadium tetrachloride, aluminum trichloride, alkylaluminum dihalides, alkylaluminum sesquihalides and dialkylaluminum halides. Of these, titanium tetrachloride and aluminum halides such as aluminum trihalide and alkylaluminum dihalides are preferable. The amount of the releasing agent used is preferably 5 times or less the molar amount of titanium in the liquid.

Further, as in Japanese Patent Application Nos. 57-121745 and 57-123698, an improved formulation such as a method of adding titanium tetrachloride or titanium tetrachloride and an electron-donating compound upon precipitation of liquefied titanium trichloride is also a preferable method. Is.

In the method of the present invention, the solid titanium trichloride catalyst complex as described above is used as a catalyst. Titanium tetrachloride, pure titanium trichloride (TiCl ₃ ) obtained by hydrogen reduction of titanium tetrachloride, titanium trichloride-aluminum trichloride eutectic obtained by aluminum reduction of titanium tetrachloride (TiCl ₃
Such as ₃ · 1/3 AlCl ₃₎ and mechanical grinding thereof titanium trichloride, the intact, not remarkable effect of the present invention as described below, not suitable as a catalyst in the present process.

The organoaluminum-based cocatalyst used in the present invention is triethylaluminum, trinormalpropylaluminum, or trinormalhexylaluminum.

In general, in the polymerization of propylene, when the above-mentioned trialkylaluminum is used as a cocatalyst, usually only a polymer having extremely low stereoregularity can be obtained. Therefore, it is essential to use the third component in combination. A sufficiently high stereoregular polymer can be obtained without using the third component.

Further, diethylaluminum monochloride, which gives high stereoregularity in the polymerization of propylene, does not give a stereoregular polymer of trialkylaluminum or higher in the method of the present invention, and the molecular weight of the produced polymer is low, so that it is a polymer. However, there are drawbacks such as low mechanical strength and low polymerization activity.

The third component of the catalyst is not usually required as described above, but an electron-donating compound can be used as the third component for the purpose of slightly improving stereoregularity.

Such electron-donating compounds include compounds containing one or more electron-donating atoms or groups, for example, ethers, polyethers, alkylene oxides, furans, amines, trialkylphosphines, triarylphosphines, pyridines. , Quinolines, phosphoric acid esters, phosphoric acid amides,
Phosphine oxide, trialkyl phosphite, triaryl phosphite, ketone, carboxylic acid ester,
Examples thereof include carboxylic acid amide. Of these, preferred are ethyl benzoate, methyl benzoate, carboxylic acid esters such as acetic acid phenyl, glycine esters such as dimethylglycine ethyl ester, dimethylglycine phenyl ester, triphenyl phosphite, trinonyl phenyl phosphite, and the like. Triaryl phosphite etc. are mentioned.

The use ratio of each component of the catalyst is usually selected from the range of 1: 0.01 to 100, preferably 1: 0.1 to 10, in terms of molar ratio of titanium trichloride: organoaluminum catalyst in the solid titanium trichloride complex catalyst. In particular, when the organoaluminum-based catalyst is trimethylaluminum or triethylaluminum, 1: 0.01 to 1 is preferable, and when it is trinormal propylaluminum or trinormal hexylaluminum, 1: 0.2 to 20 is preferable.

Therefore, in the present invention, 3-methylbutene-1 or 3-methylbutene-1 or 3-methylbutene is present in the presence of a catalyst system comprising the solid titanium trichloride complex catalyst, an organoaluminum cocatalyst and, if necessary, a catalyst third component. Polymerize a mixture of -1 with the other olefins mentioned above.

As the polymerization method, it is possible to use the same method as other α-olefins such as ethylene, propylene and butene-1.

That is, the polymerization reaction may be carried out by gas phase polymerization or may be carried out by slurry polymerization in the presence of a solvent. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, and decane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbon solvents such as benzene and toluene.

Further, the above-mentioned olefin itself such as 3-methylbutene-1 may also be used.

The polymerization reaction can be carried out by either a batch method or a continuous method, and the polymerization temperature is usually 40 ° C to 150 ° C.
℃, preferably 60 ℃ ~ 120 ℃, in the polymerization of propylene when the polymerization temperature exceeds 70 ℃, the stereoregularity of the polymer is reduced, the yield of the crystalline polymer is reduced, in the method of the present invention Even if the polymerization temperature is high, stereoregularity does not decrease. Therefore, from the aspect of heat removal and activity of polymerization reaction, 80 ℃ ～ 100
Higher polymerization temperatures of ° C are preferably carried out. The polymerization pressure is from normal pressure to 30 atm.

During the polymerization, the molecular weight of the produced polymer can be controlled by using a known molecular weight control agent such as hydrogen or carbon halide.
Further, the solid titanium trichloride complex catalyst used as a catalyst may be used for polymerization as it is, or may be pretreated with a small amount of the above-mentioned olefin and used.

The pretreatment is at a temperature that is equal to or slightly lower than the polymerization temperature, so that the polymer produced by the pretreatment / titanium trichloride in the solid titanium trichloride complex catalyst becomes 0.1 to 10/1 (weight ratio). Done. The pretreatment can also be performed using an olefin other than 3-methylbutene-1.

The polymer of the present invention is preferably used after removing the catalyst component contained in the polymer after the above-mentioned polymerization reaction. The method for removing the catalyst component is not particularly limited, and a known method can be used. For example, a method may be used in which isobutanol is added to the polymer slurry after polymerization, treated at room temperature to about 80 ° C., and then the polymer is separated.

〔Example〕

Next, the present invention will be described more specifically with reference to Examples and Comparative Examples.

In the examples and comparative examples, the catalyst efficiency CE is the amount of 3 methylbutene-1 polymer produced (g) per 1 g of the solid titanium trichloride complex catalyst.

Further, in the present invention, the molecular weight of the 3-methylbutene-1 polymer is represented by a melt index (melt index). A low melt index indicates a high molecular weight.

The melt index (hereinafter referred to as MI) was measured by Takara Kogyo Co., Ltd. melt indexer model L211-1 320
It was measured at a temperature of 2.16 kg and a load of 2.16 kg. At this time, the measurement was carried out by adding 0.5% by weight of 9,10-dihydroanthracene as a stabilizer to the polymerized powder.

The mechanical properties of 3-methylbutene-1 polymer are ASTM
According to D638, obtained by press-molding a polymer powder to which 0.2 wt% of Irganox 1010 manufactured by Ciba-Geigy Co., Ltd., Irgafuos P-EPQ, and 0.2% by weight of 9,10-dihydroanthracene was added at 320 to 330 ° C. The film was measured.

Melting points and heats of fusion were measured by a differential calorimeter (DSC). The results of Examples and Comparative Examples are shown in Table-1.

Example 1 (A) Production of Solid Titanium Trichloride Complex Catalyst Purified toluene (165 ml) and titanium tetrachloride (165 mmol) were charged into a four-necked flask having a capacity of 500 ml and purged with dry nitrogen.
165 mmol of di-n-butyl ether was added. An orange-yellow homogeneous solution was obtained with some exotherm. While maintaining the solution at 30 ° C. under stirring, 82.5 mmol of diethylaluminum chloride was gradually added thereto to obtain a black brown titanium trichloride homogeneous solution. A uniform solution of the titanium trichloride at 30 ° C
The temperature was maintained at 40 ° C. for 30 minutes, and then the temperature was raised to 40 ° C. and stirring was continued for 2 hours, whereupon precipitation of reddish purple solid titanium trichloride was observed. At this point, 57.8 mmol of titanium tetrachloride and 19.8 mmol of methacrylic acid tridecyl ester were sequentially added, and the temperature was raised to 98 ° C. and stirring was continued for 2 hours.
Fine-purple purple titanium trichloride complex catalyst washed with 0 ml 4 times 33.
I got 0g.

(B) Polymerization of 3-methylbutene-1 A cocatalyst triethylaluminum 1.0 mmol liquefied 3-methylbutene-1 700 g was charged into a volume-2 induction stirring autoclave. When the internal temperature of the autoclave reached 80 ° C., 300 mg of the fine particulate solid titanium trichloride complex catalyst obtained in (A) above was used as titanium trichloride.
(1.95 mmol) was injected under pressure to start the polymerization reaction. After continuing the polymerization at 80 ° C. for 3 hours, 25 ml of isopropyl alcohol was charged to stop the polymerization, and unreacted monomers were expelled.

Then, 1000 ml of normal hexane was introduced, and the mixture was stirred at 50 ° C. for 30 minutes, then, the supernatant was extracted, and the catalyst component in the polymer was washed and removed. After repeating this operation 3 times, the polymer was dried to obtain 211 g of a white powdery 3-methylbutene-1 polymer. At this time, the amount of soluble polymer dissolved in normal hexane was 4.6 g. The polymer yield per 1 g of catalyst (hereinafter referred to as CE) was 720.

0.5% by weight of dihydroanthracene was added as an additive to the obtained 3-methylbutene-1 polymer, and the MI was measured at 320 ° C. and found to be 0.28. Melting point is 310 ° C, heat of fusion is 1
It was 5.0 cal / g.

Example 2 Polymerization was carried out in the same manner as in Example 1- (B) except that the polymerization temperature was 90 ° C., to obtain 307 g of a white powdery 3-methylbutene-1 polymer.

At this time, the amount of soluble polymer dissolved in normal hexane and removed was 6.2 g.

The CE was 1044 and the MI was 0.34. The melting point was 309 ° C and the heat of fusion was 14.2 cal / g.

Example 3 Example 1- (B) except that ethylene as a comonomer was intermittently supplied to the autoclave every 5 minutes to obtain a 3-methylbutene-1-ethylene copolymer having an ethylene content of 4.2% by weight. Polymerization was carried out in exactly the same manner as in (). 372 g of a powdery copolymer was obtained. CE was 907 and MI was 0.20.
The melting point was 304 ° C and the heat of fusion was 9.5 cal / g.

Example 4 Co-catalyst trinormal propyl aluminum 4.0 mmo was placed in an induction-stirring autoclave having a volume of 2 and which was replaced with nitrogen.
1, liquefied 3-methylbutene-1 700 g was charged. When the internal temperature of the autoclave reached 80 ° C., 300 mg (1.95 mmol) of titanium trichloride was used as the fine particulate solid titanium trichloride complex catalyst obtained in Example 1- (A) to perform polymerization. The reaction started. After continuing the polymerization at 80 ° C. for 3 hours, 25 ml of isopropyl alcohol was charged to stop the polymerization, and unreacted monomers were expelled. Then n-hexane 1000
After introducing ml, the mixture was stirred at 50 ° C. for 1 hour, the supernatant was extracted, and the catalyst component in the polymer was washed off. After repeating this operation 3 times, the polymer was dried to give a white powdery powder 3-
310 g of methylbutene-1 polymer was obtained. At this time, the atactic polymer dissolved in the washed normal hexane was 6.
It was 2g. At this time, the polymer yield (hereinafter referred to as CE) per 10 g of the catalyst was 1054.

Further, 0.5% by weight of dihydroanthracene was added as an additive to the obtained 3-methylbutene-1 polymer, and the MI was measured at 320 ° C. and found to be 0.080.

Example 5 Polymerization was carried out in exactly the same manner as in Example 4 except that polymerization was carried out at 90 ° C.

At that time, CE was 2055 and MI was 0.086.

Example 6 A small amount of ethylene was introduced every 5 minutes at the same time as the initiation of polymerization,
Polymerization was performed in exactly the same manner as in Example 4 except that 5% by weight of ethylene was copolymerized with respect to the total amount of polymer produced.

At this time, CE was 1370 and MI was 0.065.

Example 7 Polymerization was performed in the same manner as in Example 4 except that 8.0 mmol of trinormal hexylaluminum was used in place of trinormal propylaluminum as the cocatalyst. At this time, CE is 106
8, MI was 0.062.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1- (B) except that the cocatalyst in Example 1 was 4.0 mmol of diisobutylaluminum chloride. At that time, CE was 250 and MI was 0.18.

Comparative Example 2 Polymerization was performed in the same manner as in Example 1- (B) except that the cocatalyst in Example 1 was 4.0 mmol of diethylaluminum chloride. At that time, CE was 350 and MI was 0.89.

[Effect of the Invention] According to the method for producing a 3-methylbutene-1 polymer of the present invention, a stereoregular high molecular weight 3-methylbutene-1 polymer having excellent properties such as impact strength and elongation is obtained under high activity. Therefore, the industrial value of the present invention is great.

[Brief description of drawings]

1 and 2 are flowcharts showing one embodiment of the present invention.

Claims (2)

[Claims] 1. An aluminum content obtained by precipitating liquefied titanium trichloride in the presence of ether or thioether at a temperature of 150 ° C. or lower, and having an atomic ratio of aluminum to titanium of 0.15 or less, and a complex. Using a finely divided solid titanium trichloride complex catalyst containing an agent and triethylaluminum, trinormalpropylaluminum or trinormalhexylaluminum as an organoaluminum cocatalyst, 3-methylbutene-1 is homopolymerized with other olefins. Characterized by copolymerization 3
-Method for producing methylbutene-1 polymer. 2. When the organoaluminum is triethylaluminum, the molar ratio of titanium trichloride: organoaluminum cocatalyst in the solid titanium trichloride complex catalyst is 1: 0.01-1. Yes, when the organoaluminum-based cocatalyst is trinormal propylaluminum or trinormal hexylaluminum, the molar ratio of titanium trichloride: organoaluminum-based cocatalyst in the solid titanium trichloride complex catalyst is 1: 0.2 to 20. 3-Methylbutene-according to claim 1, characterized in that
1. Polymer production method.