JPS5854612B2 - Catalyst for polymerization, dimeric polymerization, oligopolymerization, and copolymerization of vinyl monomers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to catalysts for polymerization, particularly for the polymerization, dimerization, oligopolymerization and copolymerization of vinyl monomers having no other functional groups.

Catalysts for the polymerization, dipolymerization, oligopolymerization and copolymerization of ethylene and α-olefins consisting of an active phase, namely a transition metal compound, and various organometallic compounds attached to the surface of an inorganic or organic support are already known. ing.

When a catalyst containing an inorganic carrier is used, the ash content in the resulting polymer increases and sometimes its physical properties deteriorate.

For example, using magnesium chloride as an inorganic carrier (US Pat. No. 3,243,422 and West German Pat. No. 2,033
468), the dielectric constant of the resulting polymer is substantially impaired, leading to equipment corrosion during its processing.

Catalysts containing organic carriers have a small specific surface area and a small total pore volume, making them less effective.

Such catalysts have low specific activity (furan patent 15501).
86).

In addition, catalysts for the polymerization of ethylene and propylene consisting of compounds of transition metals from Groups 1 to 1 of the periodic table and organometallic compound cocatalysts attached to polyolefin particles having a particle size of 0.25-0.5M are also available. known (see West German patent application no. 1943751).

Using a large particle size fraction of a polyolefin such as polyethylene in the preparation of the catalyst can produce a large particle size polymer, but it is difficult to control the particle size composition of the resulting polymer.

Furthermore, other disadvantages of this catalyst include rather low specific activity, low yields and high ash content in the resulting polymer.

One of the main objectives of the present invention is to increase the specific activity of the catalyst.

Another object of the present invention is to enable control of the particle size composition of the resulting (co)polymer.

Yet another object of the present invention is to reduce the ash content in the resulting (co)polymer without washing.

The above object is to provide a polymer carrier comprising a porous copolymer of two types of vinyl monomers or a porous copolymer of a vinyl monomer and a divinyl monomer and having a specific surface area of 3030-7O0/g. Polymerization of vinyl monomers having no other functional groups, characterized in that the active phase is deposited thereon, i.e. a compound of titanium or vanadium, and optionally an organoaluminium compound cocatalyst. It is a distant relative by providing catalysts for dipolymerization, oligopolymerization and copolymerization.

As used herein, the term "porous copolymer" refers to a two-phase system consisting of a polymeric compound pierced by interconnected pores that, when submerged in an external medium, can be filled with the external medium.

If the specific surface area of the carrier is less than 307 H2/g, the activity of the catalyst will decrease, which is not preferable.

Furthermore, it is technically difficult to manufacture a body material with a specific surface area of more than 700 m2/g.

Specific pore volume Q, 3-2.8d/? Catalysts containing a support with .

A carrier having a specific pore volume of less than 0.377.9 is not preferable because it reduces the ability of the active phase, and conversely, if the specific pore volume of the carrier exceeds 2.8 cTfl/g, the carrier becomes brittle.

The catalyst is a copolymer of styrene and divinylbenzene, a copolymer of styrene and diisopropenylbenzene,
It is desirable to use a copolymer of styrene, divinylbenzene and methyl methacrylate, or a copolymer of styrene, ethyldivinylbenzene and vinylpyridine.

When the above-mentioned copolymer of vinyl monomers or copolymer of vinyl monomer and divinyl monomer is used as a carrier, the specific activity of the catalyst is substantially increased.

Preferably, the catalyst has a particle size in the range of 0.001-1 g.

Using a catalyst with a particle size in the range 0.001-IM,
It becomes possible to control the particle size and particle size distribution of the resulting polymer particles.

Preferably, the catalyst is in granulated form.

By controlling the shape of the catalyst particles, one can obtain a polymer particle morphology suitable for ensuring the most desirable hydrodynamic conditions in the reactor during the synthesis process.

The catalyst is a titanium or vanadium compound as the active phase,
More preferably it should contain titanium or vanadium chloride.

The active phase content in the catalyst is preferably 1-60% by weight.

If the content of vanadium or titanium compounds is less than 1% by weight, the activity of the catalyst will be low; on the contrary, if the content is less than 60% by weight
If the value exceeds 1, the catalytic activity of the titanium or vanadium unit prize decreases, that is, the specific activity of the catalyst decreases.

The catalyst can be prepared as follows.

The porous carrier used in the present invention is a porous copolymer obtained from two types of monovinyl monomers such as styrene, ethylstyrene, diethylstyrene, isopropylstyrene, methyl acrylate and methyl methacrylate, or a porous copolymer of such monovinyl monomers. and divinyl monomers such as divinylbenzene, ethyldivinylbenzene and diisopropenylbenzene.

Such a copolymer is produced by radical copolymerization in the presence of a pore-forming agent.

The specific surface area (m2/ & ) and specific pore volume (CTft/g) of the resulting porous copolymer depend on the composition of the monomer mixture,
Although it depends somewhat on the viscosity of the reaction medium and the stirring speed,
It is mainly defined by the type and amount of the pore-forming agent used.

As pore-forming agents, low and high molecular weight compounds are used which are well soluble in the monomer mixture, do not copolymerize and can be easily removed from the resulting copolymer.

The preparation of such porous copolymers has been introduced in many documents, and those skilled in the art will be able to appropriately set conditions such as the type and amount of the pore-forming agent, the composition of the monomer mixture, and the stirring speed. Porous copolymers used as carriers in the present invention are known per se, and are widely used mainly as carriers in chromatography and as ion exchange resins or semi-finished products thereof.

In addition, commercially available products such as Porapak (USA) and Amb
er I 1teXAD (USA)1. Servach
rom XAD (West Germany), Dawex F S
P-4022 (USA), Polysorb1 resin AH-
221, AH251, KB-410 (So), etc., can also be found as porous copolymers for use in the present invention.

The amount of titanium or vanadium compound deposited on the surface of the polymeric support can vary within any range.

However, as mentioned above, the active phase content in the catalyst is 1
-60% by weight is desirable.

To prepare catalysts based on titanium chloride, temperature -
The support is treated with titanium chloride or its solution at 70 to +180° C. in vacuum or in an inert gas atmosphere.

Catalysts based on titanium chloride have temperatures of -70 to 180
It can be prepared by treating the support successively or in combination with titanium chloride and an organoaluminium compound (or a solution thereof) at 0.degree. C. in vacuum or in an inert gas atmosphere.

The resulting catalyst is dried under vacuum at a temperature of 80-180°C.

To prepare catalysts based on vanadium chloride, the support is treated with vanadium chloride vapor or solution and then dried under vacuum.

A highly active catalyst can be obtained by using a porous copolymer with a specific surface area in the range of 3030-7O0/g as a support.

When a support with a large specific surface area is used, a catalyst having a finely dispersed crystalline phase of titanium chloride or vanadium chloride can be obtained.

This increases the efficiency of the titanium or vanadium compound and increases the activity of the catalyst.

The use of porous polymeric supports produces catalysts with high titanium or vanadium salt content.

That is, since the carrier is porous, the ability of the carrier to support titanium chloride or vanadium chloride increases.

The surface of the carrier used in the present invention coated with a titanium or vanadium compound is easily accessible to monomers and the activity of the catalyst is increased.

The catalyst according to the present invention is used for polymerization, copolymerization, dimerization and oligopolymerization of vinyl monomers having no other functional groups.

These polymerizations are carried out under pressure or reduced pressure at a monomer concentration of 0.0.
It can be carried out at 1-100% by weight and at a temperature of 70-180°C.

The reaction conditions necessary to achieve dipolymerization, oligopolymerization or higher polymerization of vinyl monomers having no other functional groups using the catalyst of the present invention are appropriately set according to well-known techniques. can do.

Generally, as is known, the higher the degree of oxidation of the transition metal and the acidity of the organoaluminum cocatalyst, and the presence of functional groups (especially ester groups) in the support, the more The degree of polymerization of the polymer becomes lower.

This fact will be clear from a comparison of conditions for dimeric polymerization, oligopolymerization, and higher-order polymerization shown in Examples below.

The use of the catalyst according to the invention increases the yield of dimers, oligomers and (co)polymers and reduces the degree of contamination by inorganic residues.

As a result, the polymer product can be used without further washing.

Another advantage of the present invention is that the particle size composition of the resulting polymer can be controlled by adjusting the particle size composition of the catalyst.

The particle size of the polymer depends on the polymer yield per unit weight of catalyst and the particle size of the support.

The yield of polymer depends on the activity of the catalyst, monomer concentration and polymerization time.

If the polymer yield is the same, ie the polymerization conditions are the same, the polymer particle size is defined by the carrier particle size.

In order to further facilitate understanding of the present invention, examples will be described which illustrate specific examples of the preparation and use of catalysts.

In Examples 1 to 27, the particle size of the catalyst was measured based on the particle size of the support.

Example 1 Preparation of catalyst Comprised of a copolymer of 70% by weight of styrene and 30% by weight of divinylbenzene, it has the form of spherical particles with a particle size of 0.3-0.8N, a specific surface area of 160 m2/g, and a specific pore size of Volume t, 6
1.18 g of carrier with 5y7ffl was placed in a dry flask.

The flask was kept under reduced pressure, and the carrier in the flask was treated with 0.15.9% titanium tetrachloride vapor and cooled.

It was then treated with vapors of 0.065.9 diethyl aluminum chloride.

The resulting catalyst was heated in vacuo to a temperature of 180°C for 3 hours.

As a result of analysis, the content of titanium chloride in the obtained catalyst was 1% by weight, and the amount of carrier was 99% by weight.

The catalyst had a spherical particle morphology. Polymerization catalyst for propylene, 15 g, diethylaluminum chloride 1.
1g, 5.7X10-3 moles of hydrogen and 13% propylene (
1 was loaded into a 300-capacity autoclave equipped with a stirrer.

Polymerization was carried out at a temperature of 60° C. and a pressure of 60 atm/g.

After 5.5 hours a polypropylene 16.9.9 with a spherical particle morphology with a particle size of 1.5-4M was obtained.

The content of the fraction insoluble in boiling n-hebutane was 86% by weight.

The polymer yield per 1 gram of titanium was 36.14 kg, and the polymer yield per 1 gram of catalyst was 112. 'l, ash content is 0
．． It was 0.046% by weight.

Example 2 Polymerization of propylene Particle size 0.1-0. obtained by the same method as in Example 1.
0.08 g of 25M catalyst, 0.76 g of diethylaluminum chloride, 5.7 x 10" moles of hydrogen and 1 mol of propylene.
30g was loaded into a 300rrLl capacity autoclave equipped with a stirrer.

Polymerization was carried out at a temperature of 60° C. and a pressure of 60 atm/g.

After 5 hours, 8 g of polypropylene was obtained in the form of spherical particles with a particle size of 0.5-1.477 m.

The yield of polymer per gram of titanium is 32 Kp, 1 catalyst!
The polymer yield per j is 100. ! i' Ash content is 0.
It was 0.052% by weight.

The molecular weight of this polypropylene was 1.5X106.

Example 3 Preparation of catalyst Comprised of a copolymer of 60% by weight of styrene and 40% by weight of divinylbenzene, it has a spherical particle morphology with a particle size of 0.5-0.9 M, a specific surface area of 2747712/,9 and a specific pore volume. 5 g of support with 1.56 m/g was placed in a dry flask.

The inside of the flask was kept under reduced pressure, and the carrier inside the flask was treated with vapor of 0.52 g of titanium tetrachloride and cooled.

The support was then treated with 0.162% diethylaluminum chloride.
g of steam.

The catalyst was heated under vacuum to a temperature of 180° C. for 3 hours.

The titanium trichloride content in the catalyst obtained as a result of analysis was 1% by weight, and the carrier content was 99% by weight.

The catalyst had a spherical particle morphology.

Polymerization of propylene 0.1 g of the above catalyst, 1 g of diethylaluminum chloride and 130.0 g of propylene. ! i' into a 3007 nl autoclave.

Polymerization of propylene was carried out at a temperature of 70° C. and a pressure of 60 atm.

After 6.6 hours, 12.8 g of polypropylene with spherical particle morphology of particle size 2.7-5, ON, were obtained.

The density of the obtained polymer particles is 0.87-0.92 j;
l/Cd.

The yield of polypropylene per gram of titanium is 41, IK
p, and the yield of polypropylene per gram of catalyst is 12
8 g, and the ash content was 0.011% by weight.

Example 4 Polymerization of propylene Particle size 0.25Q prepared by the same method as Example 3,
0.0558 g of 5w1 catalyst, 0.309 i of diethylaluminum chloride, and 130 g of propylene were charged into a 300-volume autoclave.

Polymerization was carried out at a temperature of 70° C. and a pressure of 60 atm/g.

After 7 hours, 7.3 g of polypropylene having a spherical particle morphology with a particle size of 1.5-2.8 g was obtained.

Polypropylene yield per 1g of titanium is 41.5Kp
The yield of polypropylene per gram of catalyst is 130
．． i, and the ash content was 0.0108% by weight.

Example 5 Preparation of catalyst Titanium tetrachloride 0.141:II' and diethylaluminum chloride 0.0599.9 were mixed at a temperature of -30°C and a pressure of 10-2
10077271 in w/lHg! and mixed in a volumetric flask.

The resulting mixture was composed of a copolymer of 60% by weight of styrene and 40% by weight of divinylbenzene, and had a particle size of 0.03-1.
w1. It has a spherical particle morphology with a specific surface area of 360 m2/,
! i' and a specific pore volume of 1.427/g. O
Added n.

The flask contents were kept under vacuum at a temperature of -10'C.

The resulting catalyst was kept in vacuum at a temperature of 80° C. for 10 hours.

As a result of analysis, the content of titanium chloride in the catalyst was 1% by weight, and the content of the carrier was 99% by weight.

The catalyst had a spherical particle morphology.

Polymerization of propylene The above catalyst 0.12. ! 9. 0.3 g of diethylaluminium chloride, 5.7.times.10@-3 moles of hydrogen and 130 g of propylene were charged into a stirred autoclave.

Polymerization was carried out at a temperature of 60° C. and a pressure of 60 atm/g.

After 16.5 hours, 27 g of polypropylene with particle size 0.2-0.7M spherical particle morphology was obtained.

The yield of polypropylene per 1 g-M of titanium is 72.2
Kp, and the yield of polypropylene per gram of catalyst is 2
25 g, and the ash content was 0.0023% by weight.

Example 6 Preparation of Catalyst Consisting of a copolymer of 85% by weight of styrene and 15% by weight of divinylbenzene, having a particle size of 0.03-Q, a spherical particle morphology of 1 g, a specific surface area of 9771127 g and a specific pore volume of 1.2577 0.3094 g of carrier with El was placed in the flask.

The flask was kept in vacuum, and the carrier in the flask was treated in the same manner as in Example 1 with 0.0687 g of titanium tetrachloride vapor and 0.0206 g of diethylaluminum chloride vapor.

Analysis revealed that the catalyst contained 3% by weight of titanium chloride and 97% by weight of support.

The catalyst had a spherical particle morphology.

Polymerization of propylene Above catalyst 011g1 Diethyl aluminum chloride 018
36 g and 130.9 g of propylene were charged into a 300-volume autoclave with a stirrer.

Polymerization was carried out at a temperature of 70° C. and a pressure of 60 atm/g.

After 5.9 hours, 7.8 g of polypropylene with a spherical particle morphology with a particle size of 0.15-0.45 m was obtained.

The yield of polypropylene per gram of titanium is 8.35
KP, and the ash content was 0.029% by weight.

Example 7 Preparation of a catalyst Consisting of a copolymer of 88% by weight of styrene and 12% by weight of diisopropenylbenzene, having a spherical particle morphology with a particle size of 0.250.4wl1, a specific surface area of 60 m2/g and a specific pore volume of 1 0.3301 g of carrier having .0ffl/9 was added with 0.2545.9 titanium tetrachloride in vacuum in the same manner as in Example 1.
and 0.0821 g of diethylaluminum chloride.

Analysis revealed that the catalyst contained 9.82% by weight of titanium chloride and 90.18% by weight of support.

The catalyst was in the form of spherical particles.

Polymerization of propylene 0.17 g of the above catalyst, 0.3 g of diethylaminium chloride
．． 9 and 130 g of propylene were charged into an autoclave equipped with a stirrer.

Polymerization was carried out at a temperature of 70'C and a pressure of 60 atm g.

Polypropylene 29,5, with spherical particle morphology of particle size 1524'IIrIIl after 585 hours! ? I got it.

The yield of polypropylene per gram of titanium is 5.72? and the ash content was O,OS weight %.

Example 8 Polymerization of ethylene Particle size 0.25Q prepared by the same method as Example 7,
4M Catalyst 0.1.91 Di-Technyl Aluminum Chloride 1
g and 110 g of toluene were placed in a reactor, and ethylene was added.

Polymerization was carried out at a temperature of 60° C. while keeping the ethylene pressure constant at 0.5 atm/g.

After 8.5 hours, 7 g of polyethylene with spherical particle morphology of particle size 1-2, Q7#i was obtained.

The polymerization rate of ethylene was 531 g of polyethylene/g of titanium/hour/atmospheric pressure.

Example 9 Preparation of a Catalyst It was made of a copolymer of 60% by weight of styrene, 30% by weight of divinylbenzene and 10% by weight of methyl methacrylate, had the form of spherical particles, had a specific surface area of 134 doors 2/g and a specific pore volume of 1. 0.746.9 of the support with 34 ffl/g was treated with steam of 0.0971 g of titanium tetrachloride at a temperature of 80 °C.
It was held for 5 hours.

As a result of analysis, the catalyst contained 5.6% by weight of titanium chloride and 9% of the support.
It contained 4.4% by weight.

The catalyst had a spherical particle morphology.

Oligopolymerization of propylene The above catalyst 0.095.9. 0.91 of diethylaluminum chloride and 131' of propylene were charged into the stirred autoclave.

Oligo polymerization was carried out at a temperature of 70° C. and a pressure of 60 atm/g.

After draining for 6.4 hours, 11.9 g of oligomer was obtained.

The yield of propylene oligomer per gram of titanium is 9.
1 K.

Met.

The molecular weight of the obtained olicomer was about 150.

Example 10 Dimeric polymerization of ethylene 0.007 g of catalyst obtained by the same method as in Example 9 1.08.9 g of ethylaluminum dichloride and 0
．． 2. ! li' into an autoclave with a stirrer,
Ethylene was added to this.

Trimerization polymerization was carried out at a temperature of 20'C and a pressure of 25 atm/g for 2 hours.

The ethylene pressure was kept constant during the trimerization polymerization.

The yield of butene was 94% by weight.

The yield of butene per gram of titanium was 6,100 KP.

The catalyst activity (polymer weight g/titanium tetrachloride g/time/atmospheric pressure) was 30,821.

For comparison, Example 9 was used except that no pore forming agent was used.
Specific surface area 0.03 m2/ji prepared similarly to that of
A catalyst was prepared in the same manner as in Example 9 using a carrier having
Ethylene pressurization was performed in the same manner as above.

The yield of butene per gram of titanium was 103.94 Kp.

The catalyst activity was 525.9 g of polymer/g of titanium tetrachloride/atm.

Example 11 Preparation of catalyst Comprised of a copolymer of 6.0% by weight of styrene and 40% by weight of divinylbenzene, it has a spherical particle morphology with a particle size of 0.25-0.5M, a specific surface area of 260 m2/g and a specific pore size. Volume 1
．． 0.26 g of support with 57/ji was kept in vacuum at a temperature of 80° C. for 4 hours.

This was cooled to room temperature and vanadium tetrachloride 0.153.9
treated with steam.

As a result of analysis, the vanadium chloride content was 32 weight □ and the carrier content was 68 weight %.

The catalyst had a spherical particle morphology.

Polymerization of propylene 0.045 g of the above catalyst, A7(i-44)(-9)3
0.04,9 and n-heptane 50- were charged into a stirred reactor.

Propylene was introduced into the reactor at a temperature of 60°C, and polymerization was carried out while maintaining the propylene at a constant pressure of 470'IIm and Hg.

Polypropylene 1.32.9 with a spherical particle morphology with a particle size of 2-3 shields was obtained within 2 hours.

The polymerization rate was 240 g/g titanium/hour/atmosphere.

The yield of polypropylene per gram of vanadium is 0.3
Ky.

The yield of polypropylene per gram of catalyst was 29.39.

The content of the fraction insoluble in n-hebutane was 83% by weight.

The density of the obtained polymer particles was as high as 0.9 g 7 crfl.

The molecular weight of the polymer was approximately 106.

Example 12 Polymerization of propylene Particle size 0.001 prepared by the same method as Example 11
-0.03wl1 catalyst 0.067.9. I-liisobutylaluminum 0.06.9 and n-hebutane 7
0 ml was loaded into a stirred reactor.

Propylene was introduced at a temperature of 60°C, and polymerization was carried out while maintaining the propylene pressure at a constant pressure of 4707/fflHg.

After 2 hours, 2.4 g of polypropylene in powder form with a particle size of 0.2-0.4 m were obtained.

The yield of polypropylene per gram of vanadium is 0.3
34 to 9. The yield of polypropylene per gram of catalyst is 35
．． It was i.

The polymerization rate was 270 g/vanadium/hour/atmosphere.

Example 13 Preparation of catalyst Comprised of a copolymer of 60% by weight of styrene and 40% by weight of divinylbenzene, having a spherical particle morphology with a particle size of 0.25-0.5g, a specific surface area of 260TrL2/g and a Kitamipore volume i , 5c1 ft/g was treated with 0.3i of vanadium tetrachloride vapor in a manner similar to Example 11.

The obtained catalyst was vacuum dried at a temperature of 80°C.

As a result of analysis, the content of vanadium chloride was 60% by weight, and the content of carrier was 40% by weight.

The catalyst had a spherical particle morphology.

Polymerization of propylene 0.0873g of the above catalyst, Al(IC4Hg)
30.092i and n-hebutane 70r/11 were charged to a stirred reactor.

Propylene was introduced at a temperature of 60° C., and polymerization was carried out while maintaining the propylene pressure at a constant pressure of 470 WHg.

Polymer 3 with spherical particle morphology with particle size 2-3N after 2 hours
．． 7g was obtained.

The yield of polypropylene per gram of vanadium is 0.2
It was 16Kp.

The polymerization rate was 175 g/g vanadium/hour/atmospheric pressure.

Example 14 Polymerization of ethylene Particle size 0.001 prepared by the same method as Example 11
Catalyst with -0.03N 0.046,9. 0.025 g of triisobutylaluminum and 50 g of n-hebutane were charged into a stirred reactor.

Polymerization was carried out by introducing ethylene at a temperature of 80° C. and maintaining the monomer at a constant pressure of 223 WHg.

After 3 hours, 11.1 g of polyethylene in the form of a powder with a particle size of 0.2-0.5 was obtained.

The yield of polyethylene per gram of vanadium is 2.38
The yield of polyethylene per gram of Kp1 catalyst is 241.3
It was g.

The polymerization rate was 2,700 g/g vanadium/hour/atmospheric pressure.

Example 15 Preparation of catalyst Comprised of a copolymer of 60% by weight of styrene and 40% by weight of divinylbenzene, having a spherical particle morphology with a particle size of 0.25-0.5m, a specific surface area of 2607712/, 9, and a Kitamibo volume species. A 0.90:11 support with 1.5 m''/& was treated analogously to Example 11 with vapors of 1.01.9 vanadium tetrachloride.

The resulting catalyst was kept under vacuum at a temperature of 80°C.

As a result of analysis, the vanadium chloride content was 47% by weight, and the carrier content was 53% by weight.

The catalyst had a spherical particle morphology.

The above catalyst with a polymerization particle size of ethylene of 0.25-0.5M 0.047.
9, Al(1-C4H3) 30.036 g and n
- 50 rnl of hebutane were charged to a stirred reactor.

Polymerization was carried out by introducing ethylene at a temperature of 80° C. and maintaining the monomer at a constant pressure of 223 WHg.

After 6 hours, polyethylene with spherical particle morphology of particle size 0.75-2. ! I got i'.

The yield of polymer per gram of vanadium is 0.012Ky.
Met.

The polymerization rate was 6.67j/g of vanadium/hour/atmospheric pressure.

Example 16 Polymerization of Butene Particle size 0.25- prepared by a method similar to Example 15
Catalyst with 0.5 oz. 0.02. ! 17. Triisobutylaluminum 0.042.9 and n-hebutane 17m
1 was loaded into a reactor equipped with a stirrer, and then the shielded α-butene 0
．． Added 47g.

The dilatometer was placed in a constant temperature bath at a temperature of 50°C.

After 4 hours, 0.45 g of poly-α-butene with a spherical particle morphology with a particle size of 1.5-2 w/l was obtained.

The yield of polymer per gram of vanadium was 0.5 Ky.

The polymerization rate was 41 g/g vanadium/hour/atmospheric pressure.

Example 17 Polymerization of ethylene Particle size 0.001 prepared by the same method as Example 11
-0.0188 g of catalyst with 0.03 M, 0.011 g of triisobutylaluminum. ! 300 TIl of li' and n-hebutane were charged to a stirred reactor.

Ethylene was introduced at a temperature of 80°C and polymerization was carried out while maintaining the ethylene at a constant pressure of 223 mHg.

After 25 hours, polyethylene 31' was obtained.

The yield of polymer per gram of vanadium was 20.4 Kp.

The polymerization rate was 2.78i/g of vanadium/hour/atmospheric pressure.

Example 18 Polymerization of 4-methylpentene-1 0.05 g of the catalyst prepared by the same method as in Example 5 was loaded into a dry ampoule, and (C2H5)2 IC10,
7 g and 112.5 g of 4-methylpentene were added.

The ampoule was sealed and placed in a constant temperature bath at a temperature of 50°C.

After 3.5 hours, poly-4-methylpentene-10:1 was obtained.

The yield of polymer per gram of titanium is 1.28? Met.

Example 19 Copolymerization of ethylene and propylene 0.15 g of catalyst prepared by the same method as in Example 5
1(I C4H9)2 A 7C7o, 5 g and n
-Hebutane 50- was charged into a stirred reactor.

A mixture of ethylene and propylene (mole ratio: ethylene 0.457 propylene 0.5
5) was introduced.

After 4 hours methanol was added to it.

The precipitated copolymer was separated, dried, and weighed.

The yield of a copolymer of ethylene and propylene (copolymer molar ratio: ethene 0.5/propylene 0.5) per gram of titanium was 2.121 (g).

Example 20 Preparation of catalyst Comprised of a copolymer of 60% by weight of styrene and 40% by weight of divinylbenzene, having a spherical particle morphology and a specific surface area of 36%.
12.11 g of support with 0 m2/g and a specific pore volume of 1.42 d/g were treated with titanium tetrachloride vapor according to a procedure similar to Example 9.

The titanium chloride content in the obtained catalyst was 48.5% by weight, and the catalyst had a spherical particle morphology.

Dimeric polymerization of ethylene 0.0967 g of the above catalyst, (C2H5)2AIClO,
417 g and 0.21 g of benzene were placed in an autoclave equipped with a stirrer.

At a temperature of 80°C, ethylene at a constant pressure of 25 atm/g
Dipolymerization was carried out by maintaining the temperature at

After 2 hours, the methanol in the reaction mixture was added.

The resulting product was isolated and analyzed. The yield of ethylene dimer was 32.9, of which 97% by weight was butene-1,3
The weight percent was cis-butene-2.

Example 21 Preparation of catalyst It is composed of a copolymer of 50% by weight of styrene, 20% by weight of methyl methacrylate and 30% by weight of divinylbenzene, has a spherical particle morphology, and has a specific surface area of 197 m2/! 1.08 g of support with i' and specific pore volume o, s7/g were treated with vapors of titanium tetrachloride 0.11i' and (C2H,)2klcllO,06,9 according to a procedure similar to Example 1. did.

The resulting catalyst contained 2.5% by weight of titanium chloride and had a spherical particle morphology.

Dimeric polymerization of ethylene 0.116 g of the above catalyst, (C2H5)AlC120,4
17 g and 0.21 g of benzene were charged into an autoclave equipped with a stirrer.

Dipolymerization was carried out for 2 hours at a temperature of 20° C. while maintaining the ethylene pressure at 25 atm.θ.

The yield of butene-1 was 19 g, which corresponds to an ethylene polymerization rate of 40%.

Example 22 Preparation of catalyst A catalyst was prepared following a procedure similar to Example 9.

The carrier used was made of a copolymer of 70% by weight of styrene and 30% by weight of methyl methacrylate, and had a specific surface area of 30rrL.
2/g and specific pore volume 0.97/,! i' have
The particles were irregularly shaped.

The titanium chloride content in the catalyst was 5.6% by weight.

The catalyst also had irregularly shaped particles.

Dimeric polymerization of ethylene Duplex polymerization was carried out in the same manner as in Example 20.

After 2 hours, 98 g of polyethylene and 533 g of butene were obtained.

The butenes consisted of 1638% by weight of butenes, 221.7% by weight of cis-butenes and 2145% by weight of trans-butenes.

The yield of butene per gram of titanium was 300 Ky.

Example 23 Preparation of Catalyst Support consisting of irregularly shaped particles consisting of a copolymer of 40% by weight of styrene and 60% by weight of divinylbenzene and having a specific surface area of 360 m2/g and a specific pore volume of 1.42 ffl/g. Put 7.4g into a flask, (C2H
3) Treated with 6 g of 2klJclJ.

0.4 g of the carrier thus treated was mixed with 0.3 g of the catalyst prepared in the same manner as in Example 9. ! mixed with i'.

The mixture was kept at room temperature for 2 days, then 2X 10”
Dry under MHg vacuum.

The titanium chloride content in the obtained catalyst was 38.7% by weight.

The catalyst was particulate with irregular morphology.0 Oligopolymerization of propylene 0.75 g of the above catalyst, (C2H3)2Alcl 1.4
,! 9 and 400 g of propylene were charged into an autoclave equipped with a stirrer.

Polymerization was carried out at a temperature of 70°C. After 4 hours, 14 g of propylene oligomer was obtained.

Example 24 Preparation of catalyst Comprised of a copolymer of 50% by weight of styrene, 20% by weight of 4-vinylpyridine and 30% by weight of commercially available divinylbenzene, having a spherical particle morphology with a particle size of 0.2-0.7g, and a specific surface area of 4 g of a support having a specific pore volume of 176 m27 & and a specific pore volume of 1,2 crflll & titanium tetrachloride o, s! according to a procedure similar to Example 1. ! and (C2H5) 2 people were treated with 125 g of 1C.

The titanium chloride content in the obtained catalyst was 6% by weight.

The catalyst had a spherical particle morphology. Polymerization of propylene The above catalyst 0.4,9. Triethyl aluminum 0.
2 g and 130 g of propylene were placed in an autoclave with a stirrer.

Polymerization was carried out at a temperature of 70°C for 2 hours.

The yield of polypropylene is 33g, its particle size is 1-4wl
1 and the product had a spherical particle morphology.

Example 25 Preparation of catalyst Comprised of a copolymer of 70% by weight of styrene and 30% by weight of divinylbenzene, having a spherical particle morphology with a particle size of 0.035-0.08 g, a specific surface area of 700 m27 g and a specific pore volume of 0.3. Support 3. with m3/, 9. Example 1 of FM
It was treated with 0.37 g of titanium chloride and 0.15 g of diethylaluminum chloride according to a similar procedure.

The resulting catalyst contained 7% by weight of titanium chloride and had a spherical particle morphology with a particle size of 0.035-0.089.

Oligopolymerization of propylene 0.14 g of the above catalyst, 0.1 g of diethylaluminum chloride.
21,! i' and 130 g of propylene were charged into an autoclave equipped with a stirrer.

Oligo polymerization was carried out at a temperature of 70'C for 2 hours.

The yield of cut propylene oligomer was 5 g.

Example 26 Preparation of Catalyst A support in the form of spherical particles consisting of a copolymer of styrene 70 wt.
26. ! The i+ was kept under vacuum for 4 hours at a temperature of 80° C., cooled to room temperature and treated roughly with vanadium tetrachloride vapor.

The resulting catalyst was kept under a vacuum of IQ-3m) (g) at a temperature of 80°C.

The vanadium chloride content in the obtained catalyst was 31.1% by weight.

The catalyst had a spherical particle morphology. Polymerization of alpha-butene The above catalyst 0.02. ! i+, IJ Isobutyl aluminum 0.042,91 n-hebutane 17- and liquid alpha-butene 0.4'# were inserted into a dilatometer with a stirrer.

This dilatometer was placed in a constant temperature bath at a temperature of 50'C. After 4 hours of polymerization, 0.45 g of poly-α-butene was obtained.

This yield is 225 g of polymer per vanadium duram.
corresponds to

Example 27 Preparation of catalyst A catalyst was prepared following a procedure similar to Example 26.

The carrier used was a copolymer of 40% by weight of styrene and 60% by weight of divinylbenzene, and had a particle size of 0.035-0.
．． 08 plate spherical particle morphology, specific surface area 500777
-2/g and a Kitamibore volume of 2.8 crfl/g.

The content of vanadium chloride in the obtained catalyst was 10% by weight.
Met.

The catalyst had a spherical particle morphology.

Polymerization of propylene Above catalyst 0.30:111 N isobutylaluminum 0.05. F and n-heptane 50- were charged to a stirred reactor.

Propylene was introduced at a temperature of 60° C., and polymerization was carried out while maintaining the propylene pressure at a constant pressure of 470 WHg.

Polymerization time was 6 hours.

The yield of polypropylene was 1.46 g, and the product had a spherical particle morphology with a particle size of 0.15-0.35 m.

The polymerization rate of propylene was 40 g/g vanadium/hour/atmospheric pressure.

Example 28 Ethylene and propylene were polymerized using the catalyst prepared in Example 11 in the same manner as in Example 11.

However, the polymerization temperature was 70°C, and the monomer pressure was 240WH.
It was held at g.

The activity of the catalyst (expressed as a polymerization rate) was as shown in Table 1 below.

For comparison, Table 1 also shows the results of polymerization conducted without using a porous copolymer carrier.

Example 29 3 shown in Table 2 below prepared by the same method as Example 7
Liquid polypropylene was polymerized in an autoclave in the same manner as in Example 7 using a seed catalyst.

The concentration of diethylaluminum chloride in the polymerization solution is 19/
1, the polymerization concentration was 70°C, and the polymerization time was 6 hours.

The polymer yield per gram of titanium was as shown in Table 2.

Example 30 A catalyst was prepared in the same manner as in Example 1.

However, a carrier which is a spherical particle with a particle size of 0.25 to 0.315 w1 l was used.

The titanium trichloride content in the obtained catalyst was 4.2% by weight.

Using this catalyst, propylene was polymerized under the same conditions as in Example 1.

However, triethylaluminum was used instead of diethylaluminum chloride.

A polypropylene with a spherical particle morphology with a particle size of 1.5-1.6 m was obtained.

Polymer yield per gram of titanium is 18.1 Ky, catalyst 1
The polymer yield per g is 235. ,@Met.

Claims (1)

[Scope of Claims] A polymer comprising a porous copolymer of 12 types of vinyl monomers or a porous copolymer of vinyl monomers and divinyl monomers and having a specific surface area of 30-70071127 g Polymerization of vinyl monomers with no other functional groups, characterized in that the active phase consists of a titanium or vanadium compound deposited on a support and optionally an organoaluminum compound cocatalyst. Catalyst for dimerization, oligopolymerization and copolymerization. 2 The specific pore volume of the carrier is 0.3-2.8 crf17 g
The catalyst according to claim 1, which is 3. The catalyst according to claim 1 or 2, wherein the carrier is a copolymer of styrene and divinylbenzene. 4. The catalyst according to claim 1 or 2, wherein the carrier is a copolymer of styrene and diisopropenylbenzene. 5. The catalyst according to claim 1 or 2, wherein the carrier is a copolymer of styrene, divinylbenzene and methyl methacrylate. 6. The catalyst according to claim 1 or 2, wherein the carrier is a copolymer of styrene, ethyldivinylbenzene and vinylpyridine. 7. The catalyst according to any one of claims 1 to 6, which is in granular form. 8. Claim 1 in which the particle size is 0.001-1m
The catalyst according to any one of Items 1 to 7. 9. The catalyst according to any one of claims 1 to 8, wherein the titanium or vanadium compound is a chloride of each. 10. A catalyst according to any one of claims 1 to 9, wherein the content of active phase is 1 to 60 □ by weight.