EP1339759A4 - PREPOLYMERIZATION METHOD OF $g(a)-OLEFIN - Google Patents

PREPOLYMERIZATION METHOD OF $g(a)-OLEFIN

Info

Publication number
EP1339759A4
EP1339759A4 EP01981108A EP01981108A EP1339759A4 EP 1339759 A4 EP1339759 A4 EP 1339759A4 EP 01981108 A EP01981108 A EP 01981108A EP 01981108 A EP01981108 A EP 01981108A EP 1339759 A4 EP1339759 A4 EP 1339759A4
Authority
EP
European Patent Office
Prior art keywords
catalyst
prepolymerization
inert solvent
olefin
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01981108A
Other languages
German (de)
French (fr)
Other versions
EP1339759A1 (en
Inventor
Woo-Kyoung Kim
Kun Lo
Il-Seop Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hanwha General Chemicals Co Ltd
Original Assignee
Samsung General Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samsung General Chemicals Co Ltd filed Critical Samsung General Chemicals Co Ltd
Publication of EP1339759A1 publication Critical patent/EP1339759A1/en
Publication of EP1339759A4 publication Critical patent/EP1339759A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound

Definitions

  • the present invention relates to a method for the prepolymerization of ⁇
  • the present invention relates to a prepolymerization method which can be
  • the ⁇ -olefin prepolymer was fed in the reactor by using a pump after diluted into a
  • the present invention is directed to solve the above mentioned problems,
  • an inert solvent having high viscosity with molecular weight of 300g/mole or more is
  • reaction medium used as a reaction medium.
  • Mineral oil is especially preferred as a reaction medium.
  • inventions may be a typical Zieglar-Natta type catalyst described in U.S Patent Nos.
  • preparation method which is, comprises the following steps:
  • inventions include one or more compounds selected from the group consisting of
  • trialkylaluminium such as triethylaluminium or tributylaluminium
  • trialkenylaluminium such as triisoprenylaluminium, partially alkoxylated
  • alkyaluminium including dialkylaluminiumalkoxide such as
  • alkylaluminiumsequialkoxide such as ethylaluminiumsequiethoxide or
  • butyaluminiumsequiethoxide, partially halogenated aluminium including
  • alkylaluminiumdihalide such as ethylalumniumdichloride, propylaluminiumdichloride or butylaluminiumbromide, dialkyaluminiumhydride
  • alkoxylated halogenated alkylaluminium such as ethylaluminiumethoxychloride
  • An inert solvent with comparably low viscosity such as hexane, heptane and
  • kerocene is typically used as a reaction medium when the prepolymerization is
  • inert solvent used in the present invention is desirably 50 to lOOcst (centistokes) at
  • reaction vessel it is uniformly mixed with grease having high viscosity with
  • reaction uniformity can be improved, and also the prepolymers can be uniformly
  • a desirable ratio of the solid complex titanium catalyst (a) is titanium atom
  • the inert solvent a desirable ratio of organometal, especially aluminium atom, in the
  • organometallic compound (b) component is about 0J to 100 moles, preferably about
  • reaction conditions should be selected after considering the liquid
  • the prepolymerization temperature is preferably about 10 to 100 °C , more
  • Pressure is preferably about 50 atm or less, more
  • solubility of ⁇ -olefins, etc. preferably, 30 minutes to 5 hours.
  • Fig. 1 shows the feed uniformity and the change in temperature of the
  • reaction medium was agitated for about 30 minutes, propylene was fed thereto.
  • prepolymerization was conducted, while the reaction temperature was maintained at 0 °C and the propylene was fed in at the flow rate of 2g/min for 2.5 hours.
  • the precipitation level was compared with respect to three types of slurries
  • Sample 3 (comparative example) Prepolymer slurry in hexane.
  • prepolymer slurry in oil and grease were mixed, but most of the prepolymer slurry in
  • titanium atom (g-aluminium/g-titanium) became 4, and also the Si-type electron
  • Fig. 1 shows that the feeding rate was not uniform and thereby the reaction

Abstract

The present invention relates to a method for the prepolymerization of α-olefin in the presence of a catalyst system which comprises (a) a magnesium supported solid complex titanium catalyst and (b) an organometallic compound of metal of Group I or III of the Periodic Table, characterized in that an inert solvent having high viscosity with molecular weight of 300g/mole or more is used as a reaction medium.

Description

PREPOLYMERIZATION METHOD of α-OLEFIN
TECHNICAL FILED
The present invention relates to a method for the prepolymerization of α
-olefin in the presence of (a) a magnesium supported solid complex titanium catalyst
and (b) an organometallic compound of metal of Group I or III of the Periodic Table,
characterized in that an inert solvent having high viscosity with molecular weight of
300 g/mole or more is used as a reaction medium.
The present invention relates to a prepolymerization method which can be
used in the uniform feeding of prepolymers with large diameter into a reactor, and
thereby the present invention is useful when there is non-uniformity in concentration
caused by precipitation of prepolymer due to its particle's large diameter, e.g, 100
μm or more, and when there is a plugging in a high pressure pump when it is fed into
a small scale reactor such as in pilot scale.
DISCLOSURE OF INVENTION
The prepolymerization of α-olefin was conventionally conducted at room
temperature using an inert liquid solvent with low molecular weight (lOOg/mole or
less) and low viscosity such as hexane and heptane as a reaction medium, and then
the α-olefin prepolymer was fed in the reactor by using a pump after diluted into a
slurry state in the storage drum. In this process, when the α-olefin prepolymer has a
large diameter (100 μm or more), it precipitates within the storage drum and thereby varying its concentration within the storage drum as the feeding time elapses. Further,
when a commercial quantitative pump, which is typically in use for feeding a small
amount of α-olefin prepolymer into a small scale reactor such as in pilot scale, is
used, it induces a frequent abnormal feeding, because of its particle's large diameter
e.g. lOOjMii or more.
The present invention is directed to solve the above mentioned problems,
and the purposes of the present invention are to provide a prepolymerization method
of α-olefin which is capable of preventing abnormal feeding and improving reaction
uniformity by conducting the reaction within a reaction medium with molecular
weight of 300g/mole or more and high viscosity such as mineral oil.
The prepolymerization method of α-olefin according to the present
invention, which is conducted in the presence of a catalyst system which comprises
(a) a magnesium supported solid complex titanium catalyst and (b) an organometallic
compounds of metal of Group I or III of the Periodic Table, is characterized in that
an inert solvent having high viscosity with molecular weight of 300g/mole or more is
used as a reaction medium. Mineral oil is especially preferred as a reaction medium.
The magnesium supported solid titanium catalyst (a) used in the present
invention may be a typical Zieglar-Natta type catalyst described in U.S Patent Nos.
4,482,687, 4,277372, 3,642,746, 3,642,772, 4,158,642, 4,148,756, 4,477,639,
4,518,706, 4,946,816, 4,866,022, 5,013,702, 5,124,297, 4,330,649, European Patent
No. 131,832 or Japanese Patent Publication No. Sho 63-54004, etc. A preferable example of the magnesium supported solid titanium catalyst (a)
used in the present invention is a catalyst prepared by a simple and efficient
preparation method, which is, comprises the following steps:
(i) preparing a solution containing magnesium by dissolving a magnesium
compound having no reducibility such as magnesium halide and a Group II-IA
compound of the Periodic Table into the solvent mixture of cyclic ether, one or more
of alcohol, a phosphorus compound and organosilane;
(ii) precipitating solid particles by reacting said solution containing
magnesium with a transition metal compound, a silicone compound, a tin compound
or the mixture thereof; and then
(iii) reacting said precipitated solid particles with a titanium compound and
an electron donor, and then obtaining solid catalyst particles having regulated shapes
after washing said reaction product with hydrocarbon solvents.
Preferable examples of the organometallic compound (b) used in the present
invention include one or more compounds selected from the group consisting of
trialkylaluminium such as triethylaluminium or tributylaluminium,
trialkenylaluminium such as triisoprenylaluminium, partially alkoxylated
alkyaluminium including dialkylaluminiumalkoxide such as
diethylaluminiumethoxide or dibutyaluminiumbutoxide and
alkylaluminiumsequialkoxide such as ethylaluminiumsequiethoxide or
butyaluminiumsequiethoxide, partially halogenated aluminium including
alkylaluminiumdihalide such as ethylalumniumdichloride, propylaluminiumdichloride or butylaluminiumbromide, dialkyaluminiumhydride
such as diethylaluminiumhydride or dibutylaluminiumhydride and partially
alkoxylated halogenated alkylaluminium such as ethylaluminiumethoxychloride,
butylaluminiumbutoxychloride or ethylalurmniumethoxybromide, more preferably,
trialkylaluminium.
An inert solvent with comparably low viscosity such as hexane, heptane and
kerocene is typically used as a reaction medium when the prepolymerization is
conducted in the liquid state, but in the present invention an inert solvent, especially
with molecular weight of 300g/mole or more and comparably high viscosity is used
as a reaction medium, thus the phenomenon in which prepolymers precipitate after
the completion of prepolymerization can be suppressed. The viscosity range of the
inert solvent used in the present invention is desirably 50 to lOOcst (centistokes) at
40 TJ .
Further, in the present invention, when the prepolymer is fed into the
reaction vessel, it is uniformly mixed with grease having high viscosity with
appropriate ratio so that the prepolymers could not precipitate even in the long-term
storage, and then said uniformly mixed mixture with high viscosity is uniformly fed
into the reaction vessel by using a metering pump appropriate for fluid with high
viscosity. Thus, the abnormal feeding into the reaction vessel can be avoided, then
reaction uniformity can be improved, and also the prepolymers can be uniformly
distributed without being precipitated.
For the prepolymerization in the liquid state according to the present invention, a desirable ratio of the solid complex titanium catalyst (a) is titanium atom
of about 5 to 500 mmole, preferably about 10 to 100 mmole on the basis of 1 liter of
the inert solvent, a desirable ratio of organometal, especially aluminium atom, in the
organometallic compound (b) component is about 0J to 100 moles, preferably about
0.5 to 50 moles on the basis of titanium atom of 1 mole in the catalyst (a).
The prepolymerization method of α-olefin of the present invention proceeds
in the same manner as the prepolymerization method of olefin using conventional
Ziegler-type catalysts. Especially, the prepolymerization is conducted in the absence
of oxygen and water. In the prepolymerization of the present invention using an inert
solvent with molecular weight of 300g/mole or more and high viscosity as a reaction
medium, the reaction conditions should be selected after considering the liquid
viscosity of said inert solvent and the solubility of α-olefins to the reaction medium,
etc. The prepolymerization temperature is preferably about 10 to 100 °C , more
preferably about 30 to 80 °C . Pressure is preferably about 50 atm or less, more
preferably about 0J to 10 atm. The time for the prepolymerization is determined
after considering the desirable degree of the prepolymerization, catalyst activity and
solubility of α-olefins, etc., preferably, 30 minutes to 5 hours.
According to the α-olefin prepolymerization method of the present
invention, the concentration uniformity and feeding stability of the slurry of a
catalyst with a large diameter of 100 jwn or more and, thereby the polymerization
stability of the polymerization reaction and quality uniformity of the final product may be improved.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows the feed uniformity and the change in temperature of the
reactor according to one preferred example of the α-olefin prepolymerization
method of the present invention.
BESTMODEFORCARRYINGOUT THEINVENTION
The present invention is described in detail according to the examples and
comparative examples, but the scope of the present invention is not limited by these
examples and comparative examples.
Example 1
Prior to the prepolymerization, mineral oil to be used herein was added to a
flask, and heated to 100 °C while it was agitated for 12 hours or more in a nitrogen
atmosphere in order to remove moistures contained in the mineral oil. A 4-liter
polymerization reactor equipped with a mechanical agitator and a cooling/heating
jacket was prepared into the nitrogen atmospheric condition, and then 1,300ml of
mineral oil as a reaction medium, lOOg of titanium catalyst and 150mmol of
triethylaluminium were fed into the reactor in sequence. The reaction temperature
was raised to 40 °C while the reaction medium was agitated at 350rpm. After the
reaction medium was agitated for about 30 minutes, propylene was fed thereto. The
prepolymerization was conducted, while the reaction temperature was maintained at 0 °C and the propylene was fed in at the flow rate of 2g/min for 2.5 hours.
Example 2
The precipitation level was compared with respect to three types of slurries
as follows:
Sample 1: Prepolymer slurry in oil prepared in Example 1 + grease
(oil/grease =2/1 weight ratio).
Sample 2: Prepolymer slurry in oil prepared in Example 1 + grease
(oil/grease =3/1 weight ratio).
Sample 3: (comparative example) Prepolymer slurry in hexane.
(1) For the above three samples, the degree of prepolymerization was 3
(g-PP/g-catalyst), and the concentration was 20 weight percent.
(2) The above three samples were respectively added into a glass bottle with
7cm of diameter to 100mm height while the samples were uniformly agitated.
(3) Each of the bottles containing the slurry samples was uniformly mixed,
and then the precipitation depth was measured as a function according to the time
after it was left in a vessel at 0 °C .
Table 1. Comparison of precipitation depth by types of solvents and as a
function to the time (unit: mm)
Table 1 shows that there was no precipitation until 5 days when the
prepolymer slurry in oil and grease were mixed, but most of the prepolymer slurry in
the hexane slurry was precipitated within 5 minutes.
Example 3
The feeding stability in a continuous polypropylene polymerization reactor
in a pilot scale was compared with those of the prepolymer prepared in the same
manner as the composition of the prepolymer slurry in oil + grease mixture
(oil/grease = 2/1 weight ratio) experimented in the above EXAMPLE 2 and the
prepolymer slurry in hexane.
<Polymerization conditions and procedures>
(1) 30kg of liquid propylene was added to a 150 Liter polymerization reactor
equipped with an agitator.
(2) The reaction temperature was controlled to 67 °C , and hydrogen was fed
thereto until the pressure rose to 30kg/cm2.
(3) The prepolymer was fed at the amount of lg-titanium per 1 hour, and the
triethylaluminium was continuously fed thereto until the ratio of aluminium to
titanium atom (g-aluminium/g-titanium) became 4, and also the Si-type electron
donor was continuously fed thereto until the ratio of silicone to titanium atom
(g-silicone/g-titanium) became 3.5.
(4) The prepolymer slurry in oil + grease mixture was fed into the reactor by using a piston-type pump, and the prepolymer slurry in hexane was fed into the
reactor by using a reciprocating metering pump.
(5) The feeding uniformity and the change in temperature of the reactor in
the two above cases were measured, and the results are shown in Fig 1.
Fig. 1 shows that the feeding rate was not uniform and thereby the reaction
temperature severely fluctuated in the case of feeding the prepolymer slurry in
hexane into the reactor, while the feeding rate was uniform and thereby the reaction
temperature was relatively uniform in the case of feeding the'prepolymer slurry in oil
plus grease into the reactor.
In conclusion, the phenomena, in which the prepolymers become
precipitated after the completion of prepolymerization, was reflectively suppressed,
and thereby the abnormal feeding was prevented, and the uniformity of the reaction
was improved by using the prepolymerization method according to the present
invention.

Claims

WHAT IS CLAIMED IS;
1. A prepolymerization method of α-olefin in the presence of a catalyst system
which comprises (a) a magnesium supported solid complex titanium catalyst and (b)
an organometallic compound of metal of Group I or III of the Periodic Table,
wherein an inert solvent of high viscosity with molecular weight of 300g/mole or
more is used as a reaction medium.
2. The method of Claim 1, wherein the inert solvent is mineral oil.
3. The method of Claim 1, wherein the viscosity of said inert solvent is in the range
of 50 to 100 centistokes at 40 °C .
4. The method of any one of Claims 1 to 3, wherein said organometallic compound is
trialkylaluminium.
5. The method of any one of Claims 1 to 3, wherein the ratio of said solid complex
titanium catalyst (a) to the inert solvent is 5 to 500 millimoles of titanium atoms per
one liter of the inert solvent, and the ratio of organometals in the organometallic
compound (b) component to the catalyst (a) is 0J to 100 moles per one mole of
titanium atoms in the catalyst (a).
EP01981108A 2000-11-09 2001-10-18 PREPOLYMERIZATION METHOD OF $g(a)-OLEFIN Withdrawn EP1339759A4 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR2000066410 2000-11-09
KR10-2000-0066410A KR100389961B1 (en) 2000-11-09 2000-11-09 α-olefin prepolymerization method
PCT/KR2001/001757 WO2002038622A1 (en) 2000-11-09 2001-10-18 PREPOLYMERIZATION METHOD OF α-OLEFIN

Publications (2)

Publication Number Publication Date
EP1339759A1 EP1339759A1 (en) 2003-09-03
EP1339759A4 true EP1339759A4 (en) 2006-03-29

Family

ID=19698064

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01981108A Withdrawn EP1339759A4 (en) 2000-11-09 2001-10-18 PREPOLYMERIZATION METHOD OF $g(a)-OLEFIN

Country Status (5)

Country Link
EP (1) EP1339759A4 (en)
JP (1) JP2004513991A (en)
KR (1) KR100389961B1 (en)
CN (1) CN1210311C (en)
WO (1) WO2002038622A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100389961B1 (en) * 2000-11-09 2003-07-02 삼성종합화학주식회사 α-olefin prepolymerization method
KR20070091444A (en) * 2006-03-06 2007-09-11 주식회사 엘지화학 Polymerization method of propylene comprising olefin pre-polymerization step
KR101115671B1 (en) * 2007-03-28 2012-02-15 주식회사 엘지화학 Prepolymer catalyst for prepareing high-density polyolefin, preparation method thereof, and method for preparing high-density polyolefin using the prepolymer catalyst
KR101486135B1 (en) * 2013-04-03 2015-01-23 삼성토탈 주식회사 A manufacturing method of a diluted catalyst for a polymerization of olefin and a process for preparation of polyolefin using the diluted catalyst
CN106414520A (en) * 2014-06-02 2017-02-15 Sabic环球技术有限责任公司 Procatalyst for polymerization of olefins comprising monoester and amidobenzoate internal donor
CN113214417B (en) * 2021-03-09 2023-06-06 中国石油化工股份有限公司 Method for preparing polypropylene by using metallocene catalyst

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US3642746A (en) * 1968-08-01 1972-02-15 Mitsui Petrochemical Ind Process for the polymerization and/or copolymerization of olefins with the use of ziegler-type catalysts supported on carrier
US4482687A (en) * 1979-10-26 1984-11-13 Union Carbide Corporation Preparation of low-density ethylene copolymers in fluid bed reactor
EP0415588A1 (en) * 1989-08-29 1991-03-06 BP Chemicals Limited Process for preparing in gas phase elastomeric copolymers of propylene
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JP3854316B2 (en) * 1993-02-17 2006-12-06 チッソ株式会社 Method for producing polyolefin

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US3642746A (en) * 1968-08-01 1972-02-15 Mitsui Petrochemical Ind Process for the polymerization and/or copolymerization of olefins with the use of ziegler-type catalysts supported on carrier
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EP0588277A2 (en) * 1987-02-02 1994-03-23 Fina Technology, Inc. Process for increasing the efficiency of a pre-polymerized catalyst
EP0415588A1 (en) * 1989-08-29 1991-03-06 BP Chemicals Limited Process for preparing in gas phase elastomeric copolymers of propylene
US5948872A (en) * 1990-04-13 1999-09-07 Mitsui Chemicals, Inc. Solid titanium catalyst component for olefin polymerization olefin polymerization catalyst prepolymerized polyolefin-containing catalyst and method of olefin polymerization
JP3854316B2 (en) * 1993-02-17 2006-12-06 チッソ株式会社 Method for producing polyolefin
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Also Published As

Publication number Publication date
WO2002038622A1 (en) 2002-05-16
JP2004513991A (en) 2004-05-13
KR20020036286A (en) 2002-05-16
CN1478100A (en) 2004-02-25
KR100389961B1 (en) 2003-07-02
EP1339759A1 (en) 2003-09-03
WO2002038622A8 (en) 2003-05-01
CN1210311C (en) 2005-07-13

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