US 7,009,012 B2 · Supported catalyst for producing syndiotactic styrenic polymer

Abstract

The present invention provides a supported catalyst comprising (A) a polymer (B) a supporter, (C) a transition metal compound, and optionally (D) (a) a compound which can form an ionic complex by the reaction with the transition metal compound or (b) a specific oxygen-containing compound, and (E) an alkylaluminum compound. The supported catalyst according to present invention, which has a high activity, can be used for preparing a styrenic polymer with a high syndiotacticity. The supported catalyst can be used in combination with a cocatalyst, preferably an alkyl aluminoxane.

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Drawings

Claims24

Dependent claims

A supported catalyst comprising:

a polymer having at least one polar group;
a support having a surface that is reactive with a catalyst;
and
a catalyst comprising a transition metal compound,
wherein the polymer insulates the catalyst from the surface of the support such that the catalyst does not react with the surface of the support, and
wherein the transition metal compound is at least one compound represented by formulas I–V:
MR1aR2bR3cX4−(a+b+c) (I)
MR1dR2eX3−(d+e) (II)
where M, M1, and M2 is an atom of Group IVB;
R1, R2, and R3 are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, an aryloxy group having 1 to 20 carbon atoms, a cyclopentadienyl group, a substituted cyclopentadienyl group or an indenyl group, wherein R1, R2, and R3 may be the same or different;
X is a halogen atom;
R4, R5, and R6 are independently an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 6 to 20 carbon atoms, an arylalkylene group having 6 to 20 carbon, a cyclopentadienylene group, a substituted cyclopentadienylene group or an indenylene group, wherein R4, R5, and R6 may be the same or different;
a, b and c are an integer of 0 to 4;
d and e are an integer of 0 to 3;
and
f is independently an integer of 0 to 2.

13 more elements

A method of producing a supported catalyst comprising the steps of:

providing a polymer coating around a support, the support having a surface that is reactive with a catalyst comprising a transition metal compound, and wherein the polymer comprises at least one polar group;
adding the catalyst comprising the transition metal compound to the coated support, wherein the polymer coating insulates the catalyst from the surface of the support such that the catalyst does not react with the surface of the support, and
wherein the transition metal compound is at least one compound represented by formulas I–V:
MR1aR2bR3cX4−(a+b+c) (I)
MR1dR2eX3−(d+e) (II)
where M, M1, and M2 is an atom of Group IVB;
R1, R2, and R3 are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, an aryloxy group having 1 to 20 carbon atoms, a cyclopentadienyl group, a substituted cyclopentadienyl group or an indenyl group, wherein R1, R2, and R3 may be the same or different;
X is a halogen atom;
R4, R5, and R6 are independently an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylarylene group having 6 to 20 carbon atoms, an arylalkylene group having 6 to 20 carbon, a cyclopentadienylene group, a substituted cyclopentadienylene group or an indenylene group, wherein R4, R5, and R6 may be the same or different;
a, b and c are an integer of 0 to 4;
d and e are an integer of 0 to 3;
and
f is independently an integer of 0 to 2.

10 more elements

Dependencies are inferred from the claim text.

Description5,903 words

Summary738 words

#The present invention relates to a supported catalyst for preparing a syndiotactic styrenic polymer. More particularly, the present invention relates to a supported catalyst having high activity for preparing a styrenic polymer with a high syndiotacticity and a high crystallinity.

#Syndiotactic polystyrene (sPS) was first synthesized in 1986 (Ishihara et al., Macromolecules 1986, 19, 2464), using the homogeneous organometallic catalytic system based on a titanium compound and methylaluminoxane (MAO). Syndiotactic polystyrene is a very attractive polymer. The polymer shows a low specific gravity, a low dielectric constant, a high modulus of elasticity and an excellent resistance to chemicals. Accordingly the syndiotactic polystyrene has become a promising material for various applications in the automotive, electronic and packaging industries.

#However, the commercialization of a syndiotactic polystyrene has some serious problems, i.e. serious reactor fouling or lump, and low flowability of the product powder resulted from its unsatisfactory morphology. The problems are remained unsolvable if only using a homogeneous catalyst. These problems are solved by using a catalyst supported to an organic or inorganic support instead of using a general homogeneous catalyst on polymerization. However, the activity of a supported catalyst is generally much lower than that of the corresponding homogeneous catalyst by the order of magnitude of 2–3, and the polymerization activity of a syndiotactic polystyrene is, generally, much lower than that of polyolefin. Therefore it is very difficult to prepare a supported catalyst having acceptable activity for producing a syndiotactic polystyrene.

Brief description of the drawings1 figure

#FIG. 1 is a schematic diagram of a process for preparing a supported catalyst according to the present invention.

Detailed description5,146 words

#Catalyst System

#The present invention provides a supported catalyst comprising (A) a polymer, (B) a support, (C) a transition metal compound, and optionally (D) (a) a compound which can form an ionic complex by the reaction with the transition metal compound or (b) a specific oxygen-containing compound, and (E) an alkylaluminum compound. The detailed description of each component of a catalyst system is as follows.

#(A) Polymer

Facts

Application

10/169,330Filed 18 Dec 2000

Priority

KR 1999-6582330 Dec 1999

Published

US 2003/0109379 A112 Jun 2003

Granted

7 Mar 2006

Term ended

31 Oct 2021

Estimated · how

20 years from earliest known nonprovisional domestic filing plus recorded patent term adjustment, including 317 days of adjustment. Maintenance-fee lapses, terminal disclaimers and statutory extensions have not been checked. The continuity chain may be incomplete; this is not an enforceability determination.

Classification10 codes

C08F 10/00
Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double
C08F 4/02
Polymerisation catalysts: carriers therefor
C08F 12/08
Hydrocarbons: styrene
C08F 4/65912
Component covered by group C08F4/64 containing a transition metal-carbon bond: in combination with an organoaluminium compound

Timeline

30 Dec 1999Priority claimedKR 1999-65823
18 Dec 2000Application filedUS 10/169,330
30 Sep 2002Assigned to Samsung General Chemicals Co., Ltd.assignment of assignor's interest
12 Jun 2003PublishedUS 2003/0109379 A1
12 Sep 2003Assigned to Samsung Atofina GmbH & Co. Ltd.change of name
7 Mar 2006GrantedUS 7,009,012 B2
14 Jul 2014Assigned to Samsung Total Petrochemicals Co., Ltd.change of name
3 Sep 2015Assigned to Hanwha Total Petrochemical Co., Ltd.change of name
9 Nov 2015Assigned to Hanwha Total Petrochemical Co., Ltd.corrective assignment to correct the receiving party address previously recorded at reel: 036548 frame: 0271. assignor(s) hereby confirms the assignment.
31 Oct 2021Term endedEstimated, includes 317 days of adjustment

Supported catalyst for producing syndiotactic styrenic polymer

Life of this patent

Supported catalyst for producing syndiotactic styrenic polymer

Life of this patent

Life of this patent

Abstract

Drawings

Drawings

Claims24

Description5,903 words

Drawings

Classification10 codes

Life of this patent

Description5,903 words