JPH0324103A - Solid catalyst component for production of ultrahigh molecular weight polyethylene - Google Patents

Abstract

PURPOSE:To provide the title component which has high catalytic activity and excellent retentivity of activity and can give an ultrahigh molecular weight polyethylene in high yields by bringing diethoxymagnesium into contact with titanium tetrachloride in two specified stages. CONSTITUTION:Diethoxymagnesium is brought into contact with an aromatic dicarboxylic acid ester (e.g. phthalic diester) and titanium tetrachloride in the presence of an aliphatic dihalohydrocarbon (e.g. dichloroethane). The obtained composition is further brought into contact with titanium tetrachloride in the presence of an aromatic hydrocarbon (e.g. toluene) to produce a solid catalyst component. An ultrahigh molecular weight polyethylene of an average mol.wt. >=2000000 can be obtained in high yields by polymerizing ethylene by using a catalyst obtained by combining the obtained solid catalyst component with an organoaluminum compound (e.g. diethylaluminum chloride).

Description

Detailed Description of the Invention (Industrial Application Field) This invention is a high-performance solid that can obtain ultra-high molecular weight polyethylene with a weight average molecular weight of 2 million or more in high yield using a gap subjected to ethylene polymerization. It is interposed between catalyst components. (Conventional technique wI) Conventionally, La high molecular weight polyethylene has excellent impact resistance, oxidation resistance, and chemical resistance, and has self-lubricating properties, so it has been used as lining materials, various @summer materials, packing, and ski linings. It is used in a wide range of places, including skating rinks and other places. It is well known that in order to obtain such μ high molecular weight polyethylene, it is necessary to select appropriate solid etchant components and organoaluminium compounds. Recently, among solid catalyst components, it is generally known that Mg-supported Ti catalysts exhibit high activity when used in the polymerization of olefins such as ethylene and propylene. Specifically, Japanese Patent Publication No. 59-683
No. 11, I! As shown in No. 1161-286414. (Problem to be solved by the invention) However, the above-mentioned Japanese Patent Application Laid-open Nos. 59-683 11 and 6
The main constituent requirements of the solid contact component disclosed in Japanese Patent No. 1-268414 are to use magnesium chloride as a carrier material and titanium halide as an active ingredient. The chlorine contained in this magnesium chloride has the disadvantage of having an adverse effect on the produced copolymer, similar to the chlorine in titanium halogen crops, and therefore has a high activity that can virtually ignore the effect of chlorine. In addition, there was an unresolved issue that the concentration of magnesium chloride itself must be kept low.Also, when using these conventionally known solid catalyst components in the production of high molecular weight polyethylene, In many cases, the polymerization temperature is lowered in order to increase the degree of polymerization of the polymer, and as a result, the yield of the polymer per unit amount of catalyst (hereinafter referred to as catalytic activity) decreases. Therefore, a so-called deashing step for removing the residual catalyst contained in the obtained polymer and decolorizing it is not necessary. Since this demineralization process uses a large amount of alcohol or chelating agent, a recovery device or a regenerating WINK for these is indispensable, and ilfi. There are many energy and other related problems, and it is an important issue that requires immediate resolution by those skilled in the art! ! That was the issue. In addition, when these conventionally known solid catalyst components were used to produce high molecular weight polyethylene, they had the disadvantage that although their catalytic activity was high during the polymerization period, it significantly decreased as the polymerization time progressed. When a solid catalyst component is used to make a hearing aid of 13 high molecular weight polyethylene, the iit average molecular weight is 5.
The limit is about 0,000 to 2,000,000, and there is still room for improvement in the solid catalyst component itself in order to obtain a higher value.Also, because ultra-high molecular weight polyethylene has a significantly higher viscosity than general-purpose polyethylene, It is known for its poor moldability. In order to improve its moldability, the particle size of the resulting polyethylene powder must be small;
Moreover, the particle size distribution is required to be narrow. (Means for Solving the Problems) The present inventors have carried out tIi purchasing research in order to produce a solid catalyst component for the production of ultra-high molecular weight polyethylene that can solve the problems remaining in the prior art. reached an invention,
This is what I propose here. That is, this invention (a
) diethoxymagnesium, (t)) in the presence of N aliphatic dihalogenated hydrocarbon, (c) aromatic dicarbonate. An ultra-high molecular weight product characterized by contacting with an acid diester and (d) titanium tetrachloride, and further contacting the obtained ligated product with (d) titanium tetrachloride in the presence of (e) an aromatic hydrocarbon. This product provides a solid catalyst component for polyethylene production. The (b) lit dihalogenated hydrocarbon (hereinafter referred to as (b) substance) used in this invention is as follows:
Examples include methylene chloride, dichloroethane, dichlorobroban, dichlorobutane, and diprombutane. The 4(c) aromatic dicarboxylic acid diester used in this invention (hereinafter referred to as (c) substance) is preferably a phthalic acid diester, such as dimethyl phthalate, jetyl phthalate, dibrobyl phthalate, dibutyl phthalate, dibutyl phthalate, Examples include isobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethylbutyl phthalate, ethyl isobutyl phthalate, and ethylpropyl phthalate. Examples of (e) aromatic hydrocarbons (hereinafter referred to as (e) #J quality) used in this invention include toluene, xylene, and benzene. The solid catalyst component obtained in this invention constitutes a catalyst for producing high molecular weight polyethylene when used in combination with an organoaluminum compound. This explicitly used organoaluminum compound has the general formula RnA I
3-n (where R is a hydrocarbon group, X is a halogen atom,
1≦n≦3).

Specific examples include triethylaluminum, triisobutylaluminum, diethylaluminum chloride, and ethylaluminum sesquichloride, but it is also possible to use a mixture of these. When obtaining the solid catalyst component in this invention, (a) diethoxymagnesium (hereinafter referred to as (a) substance) and (b) substance are brought into contact, preferably at a temperature of 0'C to 200C for 100 hours or less. The duration is 10 hours or less. The ratio of the FD, substance (a) and substance (b) to be used is arbitrary, but it is preferable that the amount is such that a suspension can be formed.

A suspension obtained by contacting (a) the substance and (b) the substance with (c) the substance and (d) titanium tetrachloride (hereinafter (d)
) It is called a substance. ) contact conditions are usually from 50°C to 2°C.
QWR of 5 minutes or more, preferably 30 minutes or more and 100 hours or less at temperatures up to 00'C. The order in which the t* suspension liquid is brought into contact with the substances (c) and (d) is arbitrary, but it is preferable that the contact be carried out under stirring. Each component is used in any proportion, but usually (a) I? lI1gC: whereas (b
) substance t. to. 1-2g if! li1 and (
d) The substance is at least 0.1 g, preferably at least 1 g, i1! It is open. In addition, as a diluent, hydrocarbons such as hexane, heptane, decane, benzene, toluene, xylene, etc.
m medium may also be used. The contact conditions for repeatedly contacting the (d) substance with the ts solid product in the presence of the (e) substance are usually at a temperature of 50°C to 200'C for 5 minutes or more, preferably aO minutes or more and 100 hours or less. 9+1! +, (e)! Quality can be used in any proportion.
Alternatively, ζ may be washed using a lII solvent such as n-hebutane.
Both are possible. As above, l! The remaining catalyst components are combined with the organoaluminum compound to form a catalyst for producing ultra-high molecular weight polyethylene. The organoaluminum compound used has a molar ratio of 1 to 1 titanium atoms in the catalyst component.
000 i! Used in open. Polymerization is usually carried out in a hydrocarbon or halogenated hydrocarbon solution, with a polymerization temperature of 0 to 150°C and a polymerization pressure of 0 to 150°C.
It is 100kg/e+s2・G. At this time, it is also possible to add and use electron-donating compounds such as esters, ketones, amines, and silicon compounds having Si-0-C bonds, if necessary. (Operations and Effects of the Invention) When ultra-high molecular weight polyethylene is produced using the solid catalyst component obtained by this invention, the catalytic activity is extremely high and the sustainability of the activity is excellent. It has the advantage of being less likely to deteriorate in polymerization reactions that require Furthermore, because the amount of residual chlorine is so small, the effect of chlorine on the produced polymer can be reduced to such an extent that a deashing process is not required at all. Furthermore, the particle size of the polymer obtained by this invention is smaller than that of conventionally known polymers, and because the particle size distribution is narrow, it is also excellent in processability after molding. Furthermore, in addition to the catalytic properties in terms of performance, such as being able to stably produce ultra-high molecular weight polyethylene with a weight average molecular weight of 2 million or more, it also has additional effects such as reduced operational and equipment costs. It is. (Actual example) The present invention will be specifically explained below using an actual example. [Example 1] Solid catalyst component made by Ill> Nitrogen gas is sufficient for I! capacity 3, equipped with a stirrer
5g jetoxymagnesium in a 00ml round bottom flask
Then, 80 ml of 1,2-dichloroethane was charged to create a turbid state, and the mixture was treated at 20° C. for 15 minutes with stirring to obtain a slurry-like suspension. Next, this #! The residual liquid was placed in 20 ml of titanium tetrachloride at 0°C, which was placed in a 500 ml round-bottomed flask equipped with a stirrer, and the temperature inside the system was reduced to 0.
The solution was added dropwise over 30 minutes while keeping the temperature at ℃. Next, the temperature in the system was raised to 70°C and 3.0 m
1 was added, the temperature was further raised, and the reaction was allowed to proceed under reflux for 2 hours.
After that, it was washed three times with 100 ml of toluene at 90°C, and after removing the supernatant, 80 ml of toluene! Then, 20 ml of titanium tetrachloride was added, and the mixture was reacted again at 110°C for 2 hours. Finally, a solid catalyst component was obtained by washing 10 times with 200 ml of n-hebutane at 40°C. The titanium content in this solid catalyst component was 2.7% by weight, and the di-n-butyl phthalate content was 16.7% by weight. Polymerization> 700 ml of n-hebutane was charged into a stainless steel autoclave with an internal volume of 1500 ml and equipped with a stirrer, which was completely purged with ethylene gas, and triethylaluminum was added at 20°C while being kept under an ethylene gas atmosphere. 0.
70 mmol was charged. Next, 0.0052 mmol of the solid catalyst component as titanium atoms was charged, and prepolymerization was carried out at 20° C. for 30 minutes under pressure with ethylene so that the pressure in the system became I kg/c+s'·G. Thereafter, while supplying ethylene so that the pressure in the system became 4 kg/I1!1I2.G, the temperature was raised to 70°C and polymerization was carried out for 3 hours. When the obtained polyethylene powder was filtered and dried under reduced pressure, the weight was 232.5 g.
The polymer yield (hereinafter referred to as catalytic activity) per 1g"l was 25.00g/x-cat. The bulk specific gravity of the obtained polymer was 0.32z/ays", expressed as 50% of the cumulative weight. The average particle size was 140 μm. Further, the average molecular weight of this polymerer determined from the intrinsic viscosity in decalin (135°C) was 30,000 Q.
[Example 2] When the solid catalyst component in Example 1 was used and the polymerization temperature during ethylene polymerization was set to 60°C, the catalyst activity was 17.3
00g/g-cat. Met. The bulk specific gravity of the obtained polymer is 0. 31 g/c+s" and the average particle size was 130 μm. Also, the average molecular weight determined from the intrinsic viscosity of this polymer in decalin (135°C) was 4.6 million. [Example 31 Example 1 When the solid catalyst component was used and the polymerization temperature during ethylene polymerization was set to 65°C, the catalyst activity was 10.3.
00g/g-cat. Met. The bulk specific gravity of the obtained polymer is 0. 31 g/x3, and the average particle size was 110 μm. The average molecular weight of this polymer, determined from the intrinsic viscosity in decalin (135°C), was 5.9 million. [Example 4] 5 g of jetoxymagnesium and 80 ml of 1,2-dichloroethane were charged into a round bottom flask with a capacity of 300 ml, which had been thoroughly exchanged with nitrogen gas and equipped with a stirrer, and suspended. By processing at 20°C for 15 minutes with stirring, a slurry of p. A cloudy liquid was obtained. Next, this! ! 3. The suspension was placed in a 500 ml round bottom flask equipped with a stirrer and added dropwise over 30 minutes into 100 ml of titanium tetrachloride at kO ℃ while keeping the system temperature at 0 ℃.・1.5 ml of Butylphthale was added and kept for 1 hour. Next, the temperature of 4rrL in the system was raised to 90°C,
The reaction was allowed to proceed for 2 hours. Thereafter, the mixture was washed three times with 100 ml of toluene at 90°C, the supernatant liquid was removed, 80 ml of toluene and 20 ml of titanium tetrachloride were added, and the mixture was reacted again at 110°C for 2 hours. Finally, a solid catalyst component was obtained by washing 10 times with 200 ml of n-hebutane at 40°C. The titanium content in this solid catalyst component is 3. It was 0% by weight. When ethylene was polymerized using the above solid component in the same manner as in Example 1, the catalyst activity was 20.000 g/g-ca.
t. Met. The bulk specific gravity of the obtained polymer was 0.3
1 g/cm', and the average particle size was 380 μm. In addition, the average molecular weight of this polymerer determined from #!! limiting viscosity in decalin (135°C) was 2,500,000.
5g diethoxymagnesium in a 00ml round bottom flask
Then, 80 ml of 1,2-dichloroethane was charged to form a suspension, and the suspension was treated at 20° C. for 15 minutes with stirring to obtain a slurry-like suspended liquid J. Then this suspension,
The temperature inside the system was reduced to 0°C in 100ml of titanium tetrachloride at 0°C placed in a 500ml round bottom flask equipped with a stirrer.
It was added dropwise over 30 minutes while keeping the temperature at 0.0%. 75ml1ty! ．． After 7Jff, it was held for 1 hour. Next, the temperature in the system was raised to 100°C, and 2
A time reaction was performed. Then, 100ml of toluene at 90℃
After washing three times with
1 and 20 ml of titanium tetrachloride were added, and the mixture was reacted again at 110°C for 2 hours. Finally, 20 ml of n-hebutane at 40°C
A solid catalyst component was obtained by washing 10 times with 0ml. The titanium content in this solid catalyst component was 2.7% by weight. When ethylene was polymerized in the same manner as in Example 1 using the above solid component, the catalyst activity was 19,000g/
g-cat. Met. The bulk specific gravity of the obtained polymer is 0. 33g/cm', and the average particle size is 30
0)tm. Furthermore, the average molecular weight of this polymerer determined from the intrinsic viscosity in decalin (135°C) was 2.6 million. [Example 6] Capacity 30 fully purged with nitrogen gas and equipped with a stirrer
A 0 ml round bottom flask was charged with 5 g of diethoxymagnesium and 80 ml of 1,2-dichloropropane to form a suspension, and treated at 20° C. for 15 minutes with stirring to obtain a slurry of RgA liquid. Next, this suspension 8I solution was poured into 100 ml of titanium tetrachloride at 0°C, which was placed in a 500 ml round bottom flask equipped with a stirrer, while maintaining the temperature inside the system at 0°C, and then poured down to 70°C. When the mixture was heated to 90° C., 2.0 ml of diisopropyl phthalate was added, and the mixture was further heated to 90° C. and reacted for 2 hours. after that,
After washing three times with 100 ml of toluene at 90°C and removing the supernatant, 80 ml of toluene and 20 ml of titanium tetrachloride were added.
ml was added, and the reaction was again carried out at 110°C for 2 hours. After R, a solid M medium component was obtained by washing 10 times with 200 ml of n-hebutane at 40°C. The titanium content in this solid catalyst component is 3.6! There was a quantity%. When ethylene was polymerized using the above solid component in the same manner as in Practical Example 1, the catalyst activity was 24.000 g/g-ca.
t. Met. The bulk specific gravity of the obtained polymer is 0.3
3 g/(to) 3, and the average particle size was 230 am. Furthermore, the average molecular weight of this polymer determined from the intrinsic viscosity in decalin (135°C) was 2.7 million. [Example 7] A 50-liter tank fully purged with nitrogen gas and equipped with a stirrer.
A 0 ml round bottom flask was charged with 5 g of diethoxymagnesium and 80 ml of 1,2-dichloroethane to form a suspension, and the mixture was stirred at 20°C for 6 minutes. In this suspension,
By adding 2.7 ml of phthalate and treating for an additional 10 minutes, a slurry-like suspension was obtained. Next, 20 ml of titanium tetrachloride was dripped into the moat over 30 minutes while maintaining the temperature inside the system at 35°C. Next, the temperature in the system was raised and the reaction was carried out at 90°C for 2 hours. After that, 9
After washing three times with toluene room+ at 0°C and removing the supernatant, 80 ml of toluene and 20 ml of titanium tetrachloride were added.
ml and reacted again at 110°C for 2 hours k. Finally, a solid catalyst component was obtained by washing 10 times with 200 ml of n-hebutane at 40°C. The titanium content in this solid catalyst component is 3. At 0% by weight k. When ethylene was polymerized using the above solid component in the same manner as in Example 1, the catalyst activity was 30,000 g/g-ca.
t. Met. The bulk specific gravity of the obtained polymer is 0-
31 g/eII” and the average particle size is 270
It was μm. In addition, this polymer decalin (l35
The average molecular weight determined from the intrinsic viscosity in <℃> is 290
It was 10,000.

[Brief explanation of the drawing]

Figure 1 is a flowchart showing the process of this invention.

Claims (1)

[Claims] (1) contacting (a) diethoxymagnesium with (b) an aromatic dicarboxylic diester and (d) titanium tetrachloride in the presence of an aliphatic dihalogenated hydrocarbon;
A solid catalyst component for producing ultra-high molecular weight polyethylene, characterized in that the obtained composition is further brought into contact with (d) titanium tetrachloride in the presence of (e) an aromatic hydrocarbon.